Methods for using silver-containing polymeric complexes

ABSTRACT

A method can be used to provide electrically-conductive articles with electrolessly plated metal, or articles having antimicrobial properties for marine environments. The method includes disposing a silver-containing composition onto one or more supporting sides of a substrate such as continuous polymeric web. The silver-containing composition comprises a water-soluble complex of a reactive polymer with reducible silver ions, the reactive polymer comprising: (a) greater than 1 mol % of recurring units comprising sulfonic acid or sulfonate groups, (b) at least 5 mol % of recurring units comprising a pendant group capable of crosslinking via [2+2] photocycloaddition, and optionally (c) at least 1 mol % of recurring units comprising a pendant amide, hydroxyl, lactam, phosphonic acid, or carboxylic acid group. The reducible silver ions can be suitably reduced and the reactive polymer can be photoexposed to provide crosslinking in patternwise or uniform fashion.

CROSS-REFERENCE TO RELATED APPLICATIONS

Related subject matter is described and claimed in the followingcopending and commonly assigned patent applications:

U.S. Ser. No. 14/661,278 filed on Mar. 18, 2015 by Brust and Wyand andentitled “Articles with Silver-Containing Polymeric Complexes;” and

U.S. Ser. No. 14/661,235 filed on Mar. 18, 2015 by Brust, Bennett, andFalkner and entitled “Silver-Containing Compositions Containing ReactivePolymers.”

FIELD OF THE INVENTION

This invention relates to methods for using silver-containingcompositions comprising a water-soluble complex of reducible silver ionsor silver nanoparticles with a reactive polymer. Such methods can beused to provide electrolessly plated articles. Alternatively, themethods can be used to provide articles that have antimicrobialproperties, especially for marine environments. The useful reactivepolymers have pendant sulfonic acid or sulfonate groups as well aspendant groups capable of crosslinking via [2+2] photocycloaddition.

BACKGROUND OF THE INVENTION

Both silver ions and silver metal have a long history of chemical andbiological activity. In particular, some of the silver salts arephotoactive and can form catalytic silver nanoparticles on exposure tosuitable radiation. Many chemical reactions are known to be catalyzed byboth silver metal and various silver salts or silver ion complexes.Electrophilic substitutions where silver serves as a Lewis acid catalystare also known as well as organosilver compounds with chemicalreactivity.

Silver has been known for biocidal (antimicrobial) activity for over acentury and renewed interest in its biocidal properties has arisen dueto the emergence of antibiotic-resistant strains of pathogenic bacteriasuch as MERSA [see for example, Rai et al., Biotechnology Advances 27(2009) 76-83]. There is growing evidence that silver is an effectivebiocide because it can attack an organism through multiple pathways andthereby disrupt multiple critical systems such as cell wall integrityand transport, protein synthesis, and DNA and RNA replication. In spiteof the very aggressive attack by silver at the microbial level, it has along history of low toxicity to humans and other complex organisms.

Silver nanoparticles can be made without polymeric stabilizers byreducing the silver ammonium complex with sugars such as glucose ormaltose. Another frequently used method utilizes citrate to both complexthe silver ions and to act as a reducing agent. Often an additionalreducing agent such as sodium borohydride, or ascorbic acid can be usedwith the citrate. Often a surfactant or polymeric stabilizer such aspoly(vinyl pyrrolidone) or poly(ethylene glycol (PEG) is added aftersilver nanoparticles are prepared without a polymeric stabilizer.

Polymer composites with silver metal are known (Review by Dallas et al.,Advances in Colloid and Interface Science 166 (2011) 119-135); incommercial products such as antimicrobial coatings on medical devicessuch as catheters, neurological shunts (Chaloupka et al., Trends inBiotechnology, Vol. 28, No. 11, November 2010); or as coatings forcontact lens storage cases (Dantam et al., Investigative Ophthalmologyand Visual Science, Vol. 52, No. 1, January 2011). The silvernanoparticles can be formed by reducing silver ions usually provided assilver nitrate in the presence of a polymer than can peptize orstabilize the resulting silver nanoparticles to maintain a uniformdistribution and to prevent particle agglomeration or growth throughOstwald ripening effects. A variety of polymers have been reported toserve this purpose, including poly(vinyl alcohol) or PVA copolymers,poly(vinyl pyrrolidone), and poly(ethylene glycol). A polymeric catalystprepared by forming silver nanoparticles in modified polyethyleneiminehas been reported (Signori et al., Langmuir 2010, 26(22), 17772-17779).

Efforts to use naturally occurring, biodegradable, or “green” polymersin polymer-silver composites have included starch and polysaccharidesthat serve as both a stabilizing agent and a reducing agent. Silvernanoparticles showing antimicrobial behavior have been formed in thepresence of biodegradable and non-toxic chitosan derived from crabshells.

A large body of research has been focused on forming silvernanoparticles inside a network of water-soluble polymers that can becrosslinked to form a water-, ion-, and silver nanoparticle-permeablegel or hydrogel, for example using poly(acrylamide) (Uygun et al.,Macromolecular Chemistry and Physics 2009 210, 1867-1875) or copolymersderived from an acrylamide and acrylic acid [Thomas et al., Journal ofColloid and Interface Science 315 (2007) 389-395, Mohan et al., Journalof Colloid and Interface Science 342 (2010) 73-82]. Often an additionalwater-soluble polymer is present during the polymerization andcrosslinking of acrylamide to form an interpenetrating network (or IPN).For example, the formation of silver nanoparticles inpoly(acrylamide)-based IPN's is demonstrated for poly(ethylene glycol)and poly(vinyl sulfonic acid) by Mohan et al., Journal of Colloid andInterface Science 342 (2010) 73-82, and in an acrylamide-based IPN withpoly(vinylpyrrolidone) by Murthy et al., Journal of Colloid andInterface Science 318 (2008) 217-224. An acrylamide-starch IPN has beenused to form silver nanoparticles for antimicrobial purposes. A hydrogelformed from vinyl caprolactam and glycidyl methacrylate has also beenused to form antimicrobial gel containing silver nanoparticles. Hydrogelnetworks based on N-isopropylacrylamide (NIPAM) copolymerized withacrylic acid and other monomers have also shown the ability to formsilver nanoparticles with antimicrobial activity while retaining thetemperature responsive swelling behavior well known for such polymers.

The formation of silver nanoparticles in an ionic polymer orpolyelectrolyte is also known from Girard et al, Comptes Rendus Chimie16(6) 550-556, 2013 where silver nanoparticles were formed in an aqueoussolution of poly(styrene sulfonate). Silver nanoparticles formed inpoly(vinyl sulfonate) are reported in Vasilev et al., Nanotechnology 21(2010) 215102. Hydrogels prepared using copolymers derived from2-acrylamido-2-methylpropanesulfonate and vinyl pyrrolidone oracrylamide were loaded with preformed silver nanoparticles to evaluatethe antimicrobial properties (see Valle et al., Journal of AppliedPolymer Science, 2013, DOI: 10.1002/APP.38655). This art suggests thatsulfonate-bearing polymers may be useful for stabilizing silvernanoparticles.

The formation of silver nanoparticles in the presence of a polymercontaining both sulfonate and carboxylate groups is described in U.S.Pat. No. 8,828,275B2 (Wang et al.) where very highly concentrateddispersions are prepared for the purpose of forming a conductive silverink. U.S. Pat. No. 8,361,553B2 (Karandikar et al.) describes polymericsilver nanoparticle dispersions formed by reducing silver ion in thepresence of saccharinate derivatives and a variety of water-solublepolymers derived from both carboxylate and sulfonate bearing monomers.These dispersions are used to form antimicrobial surfaces on varioussubstrates. Silver nanoparticle dispersions are also described in U.S.Patent Application Publication 2009/0263496A1 (Kijlstra et al.) by firstforming silver oxide in the presence of various dispersing polymers suchas poly(vinyl pyrrolidone), poly(aspartic acid), or poly(naphthalenesulfonic acid) and reducing the silver oxide to silver with a reducingagent such as formaldehyde.

U.S. Pat. No. 7,348,365B2 (Lee et al.) described the use of gammaradiation to reduce silver ion to silver nanoparticles in the presenceof copolymers derived from vinyl pyrrolidone, acrylic acid, andacrylamide to form antimicrobial coatings. Various particles of silversalts, some specified to be less than 200 nm, are formed in the presenceof water soluble polymers such as poly(vinyl pyrrolidone) andpoly(acrylic acid) to form antimicrobial coatings or devices in U.S.Patent Application Publication 2008/0102122A1 (Mahadevan et al.) andU.S. Pat. No. 6,949,598B2 (Terry).

While there are numerous polymer-silver complexes described in the art,there remains a need for polymer-silver complexes that are water-solubleand water-coatable, but which can be crosslinked with UV light to becomewater-insoluble and highly durable after coating. There is a need forsuch polymer-silver complexes that can be readily used in antimicrobialcompositions or articles, or that can be used to form high resolutionelectrically-conductive patterns without the need for added crosslinkingagents or photoinitiators.

There is the further need to provide water-soluble polymeric complexesthat contain reducible silver ions that are readily reduced in thepolymeric complexes, before or after the polymers are crosslinked. Itwould be desirable to form silver nanoparticles in the size range of 1to 500 nm using such materials.

SUMMARY OF THE INVENTION

The present invention provides method for providing a silver-containingarticle, the method comprising:

disposing a silver-containing composition onto a first supporting sideof a substrate, the silver-containing composition comprising awater-soluble complex of a reactive polymer with reducible silver ions,the reactive polymer comprising: (a) greater than 1 mol % of recurringunits comprising sulfonic acid or sulfonate groups, (b) at least 5 mol %of recurring units comprising a pendant group capable of crosslinkingvia [2+2] photocycloaddition, and optionally (c) at least 1 mol % ofrecurring units comprising a pendant amide, hydroxyl, lactam, phosphonicacid, or carboxylic acid group, all amounts based on the total recurringunits in the reactive polymer.

The method of this invention can further comprise:

either immediately before or immediately after disposing thesilver-containing composition onto the substrate, reducing the reduciblesilver ions in the water-soluble complex to form silver nanoparticles inthe water-soluble complex.

In addition, after reducing the reducible silver ions, the method cancomprise photoexposing the water-soluble complex containing the silvernanoparticles to form a crosslinked water-insoluble complex comprisingthe silver nanoparticles, either uniformly or in a patternwise fashionon the substrate.

After photoexposing the water-soluble complex to form the crosslinkedwater-insoluble complex containing silver nanoparticles, the method cancomprise:

In some embodiments, the method further comprises:

electrolessly plating the crosslinked water-insoluble complex using anelectrically-conductive metal.

When duplex articles are to be made, the method can comprise:

disposing the silver-containing composition onto the first supportingside of a substrate,

either immediately before or immediately after disposing thesilver-containing composition onto the first supporting side of thesubstrate, reducing the reducible silver ions in the water-solublecomplex to form silver nanoparticles in the water-soluble complex on thefirst supporting side of the substrate,

disposing the same or different silver-containing composition onto anopposing second supporting side of the substrate,

either immediately before or immediately after disposing thesilver-containing composition onto the opposing second supporting sideof the substrate, reducing the reducible silver ions in thewater-soluble complex to form silver nanoparticles in the water-solublecomplex on the opposing second supporting side of the substrate, and

photoexposing the water-soluble complex containing the silvernanoparticles on either or both of the first supporting side andopposing second supporting side of the substrate, to form a crosslinkedwater-insoluble complex comprising the silver nanoparticles on either orboth of the first supporting side and opposing supporting side of thesubstrate, and

optionally, removing any remaining water-soluble complex from both thefirst supporting side and the opposing second supporting side of thesubstrate.

Such methods can further comprise:

removing any remaining water-soluble complex from both the firstsupporting side and the opposing second supporting side of thesubstrate, and

electrolessly plating the crosslinked water-insoluble complex on eitheror both of the first supporting side and the second opposing supportingside of the substrate using an electrically-conductive metal.

Such embodiments are particularly useful when the substrate is acontinuous web of transparent polymeric film having an integratedtransmittance of at least 80%.

The advantages of the present invention are provided using a uniquereactive polymer that is water-soluble or water-dispersible and can beused to form a complex with either reducible silver ions or silvernanoparticles. Two essential features are present in the reactivepolymer to provide the desired properties. The first essential featureis the presence of greater than about 1 mol % of recurring unitscomprising sulfonic acid or sulfonate groups. The second essentialfeature is the presence of at least 5 mol % of recurring unitscomprising a pendant group capable of crosslinking via [2+2]photocycloaddition group. A variety of other recurring units can bepresent in the reactive polymer, for example comprising pendant amide,hydroxyl, lactam, phosphonic acid, or carboxylic acid groups to provideadditional properties. Hydrophobic ethylenically unsaturatedpolymerizable monomers such as styrene or acrylate esters can also beused in the polymerization processes to provide polymers with enhancedfilm forming and durability.

The presence of the sulfonic acid or sulfonate groups in the reactivepolymers provide desired water solubility or water dispersibility for abroad range of uses, most importantly in the presence of reduciblesilver ions that can precipitate other less water-soluble polymers. Thependant groups that are capable [2+2] photocycloaddition provide abuilt-in crosslinking function that is only activated by exposure to theappropriate UV radiation and is extremely thermally stable.

The reducible silver ion or silver nanoparticle bearing polymericcomplexes used in this invention have a broad range of capabilities oruses due to the reactivity of the complexed reducible silver ions orsilver nanoparticles, high resolution patternability, andwater-solubility or swellability after reactive polymer crosslinking.These reducible silver ion or silver nanoparticle containing polymercomplexes can be used to form high resolution, electrically-conductivemetal grid patterns because the silver nanoparticles can act as seedcatalysts for electroless metal plating. For example, these complexescan be coated and exposed with a high resolution UV radiation anddeveloped in water, or they can be printed by various methods includinggravure or flexographic printing methods and then hardened with UV lightbefore electroless plating.

These polymeric complexes containing reducible silver ions or silvernanoparticles can also be used on various surfaces (for example, ofsubstrates) where they can be hardened or patterned with UV radiation toform silver ion loaded crosslinked hydrogels (containing reactedpolymers) wherein water and ions can diffuse in and out. Such coatingscan be used as antimicrobial coatings on various surfaces especiallysurfaces that are frequently exposed to water.

The high resolution patternability of the silver-containing polymericcomplexes described herein can enable an enhanced form of antimicrobialsurface based on recent learning about the efficacy of specificallydesigned high resolution patterns that show dramatic reduction inbiofouling and microbial colony formation without the need for metals orother toxic substances (see for example, U.S. Patent ApplicationPublication 2010/0226943A1 and U.S. Pat. No. 7,650,848 B2 and U.S. Pat.No. 7,143,709 B2 of Brennan et al.). Certain specifically designedsurface patterns can be embossed or imprinted using a layer of aspecific polymer. For example, some described patterns have minimumfeature dimensions of about 2 μm and are designated as “Sharklet AF”pattern that has been shown to have best overall performance compared tosimpler patterns with similar dimensions. The polymers used in suchpatterns are polydimethylsiloxane (PDMS) type polymers, although acrylicpolymer hydrogels have also been demonstrated (see Magin et al.,Biomacromolecules 2011, 12, 915-922).

The reducible silver ion or silver nanoparticle containingphotopatternable polymeric complexes used in this invention provide theopportunity to combine both the inherent antimicrobial activity ofsilver with the advantages of the noted essential polymer features sothat pattern formation is also enhanced, further improving theinhibition of microbial colonization and growth. In addition, the UVradiation patternability and water-solubility of the noted silver ion orsilver nanoparticle containing polymer complexes facilitate patterningin a roll-to-roll manufacturing system using simple water-bathprocessing.

DETAILED DESCRIPTION OF THE INVENTION

The following discussion is directed to various embodiments of thepresent invention and while some embodiments can be desirable forspecific uses, the disclosed embodiments should not be interpreted orotherwise considered be limit the scope of the present invention, asclaimed below. In addition, one skilled in the art will understand thatthe following disclosure has broader application than is explicitlydescribed and the discussion of any particular embodiment.

DEFINITIONS

As used herein to define various components of the silver-containingcompositions, unless otherwise indicated, the singular forms “a,” “an,”and “the” are intended to include one or more of the components (thatis, including plurality referents).

Each term that is not explicitly defined in the present application isto be understood to have a meaning that is commonly accepted by thoseskilled in the art. If the construction of a term would render itmeaningless or essentially meaningless in its context, the termdefinition should be taken from a standard dictionary.

The use of numerical values in the various ranges specified herein,unless otherwise expressly indicated otherwise, are considered to beapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as the values within the ranges.In addition, the disclosure of these ranges is intended as a continuousrange including every value between the minimum and maximum values.

Unless otherwise indicated, the term “weight %” refers to the amount ofa component or material based on the total solids of a composition,formulation, or layer. Unless otherwise indicated, the percentages canbe the same for either a dry layer or pattern, or for the total solidsof the formulation or composition.

The term “homopolymer” is meant to refer to polymeric materials thathave the same repeating or recurring unit along a polymer backbone. Theterm “copolymer” refers to polymeric materials composed of two or moredifferent repeating or recurring units that are arranged in any order(randomly or otherwise) along the reactive polymer backbone.

For the reactive polymers used in the present invention, the recurringunits can be arranged randomly along the reactive polymer backbone, orthere can be blocks of recurring units that occur naturally during thepolymerization process.

Recurring units in the reactive polymers described herein can begenerally derived from the corresponding ethylenically unsaturatedpolymerizable monomers used in a polymerization process, whichethylenically unsaturated polymerizable monomers have the desiredfunctional and pendant groups. Alternatively, desired pendant groups canbe incorporated within recurring units after polymerization ofethylenically unsaturated polymerizable monomers by reaction withrequisite precursor pendant groups.

The term “polymerization” is used herein to mean the combining, forexample by covalent bonding, of a large number of smaller molecules,such as monomers, to form very large molecules, that is, macromoleculesor polymers. The monomers can be combined to form only linearmacromolecules or they can be combined to form three-dimensionalmacromolecules that are commonly referred to as crosslinked polymers.One type of polymerization that can be carried out in the practice ofthis invention is free radical polymerization when free radicallyethylenically unsaturated polymerizable monomers and suitable freeradical generating initiators are present.

The term “reactive polymer” is used herein to refer to the copolymersdescribed below that have the essential components and propertiesdescribed and can be used in the compositions, articles, and methodsdescribed herein, and which copolymers are sensitive to ultravioletradiation so that crosslinking occurs using the pendant groups notedbelow.

In reference to reactive polymers described herein, the term“water-soluble” is used to mean that the minimum solubility in water ofa given reactive polymer is at least 0.1 weight % at 25° C. Somereactive polymers can be less water-solubility but stillwater-dispersible. The term “water-insoluble” is used to mean that agiven reactive polymer is less than less than 0.1 weight % at 25° C.

The term “crosslinked reacted polymer” is used herein to refer to thecrosslinked form of the corresponding reactive polymer.

The term “aqueous-based” refers to solutions, baths, or dispersions inwhich the predominant solvent, or at least 50 weight % of the solvents,is water.

Unless otherwise indicated, the term “mol %” when used in reference torecurring units in reactive polymers, refers to either the nominal(theoretical) amount of a recurring unit based on the molecular weightof ethylenically unsaturated polymerizable monomer used in thepolymerization process, or to the actual amount of recurring unit in theresulting reactive polymer as determined using suitable analyticaltechniques and equipment.

Unless otherwise indicated, the term “group” particularly when used todefine a substituent of a defined moiety, can itself be substituted orunsubstituted (for example and alkyl group” refers to a substituted orunsubstituted alkyl). Generally, unless otherwise specifically stated,substituents on any “groups” referenced herein or where something isstated to be possibly substituted, include the possibility of anygroups, whether substituted or unsubstituted, which do not destroyproperties necessary for the utility of the component or aqueous metalcatalytic composition. It will also be understood for this applicationthat reference to a compound of a particular general structure includesthose compounds of other more specific formula that fall within thegeneral structural definition. Examples of substituents on any of thementioned groups can include known substituents such as: halogen (forexample, chloro, fluoro, bromo, and iodo); cyano; nitro; amino; alkoxyparticularly those with 1 to 12 carbon atoms (for example, methoxy andethoxy); substituted or unsubstituted alkyl groups, particularly loweralkyl groups (for example, methyl and trifluoromethyl); alkenyl orthioalkyl (for example, methylthio and ethylthio), particularly eitherof those with 1 to 12 carbon atoms; substituted and unsubstituted aryl,particularly those having from 6 to 20 carbon atoms in the aromatic ring(for example, phenyl); and substituted or unsubstituted heteroaryl,particularly those having a 5- or 6-membered ring containing 1 to 3heteroatoms selected from N, O, S or Se (for example, pyridyl, thienyl,furyl, pyrrolyl, and their corresponding benzo and naptho analogs); andother substituents that would be readily apparent in the art. Alkylsubstituents particularly contain 1 to 12 carbon atoms and specificallyinclude “lower alkyl” that is having from 1 to 6 carbon atoms, forexample, methyl, ethyl, and t-butyl. Further, with regard to any alkylgroup, alkylene group or alkenyl group, it will be understood that thesecan be branched or unbranched and include ring (cyclic) structures.

The term “UV radiation” is used herein to refer to electromagneticradiation having a wavelength (λ_(max)) of at least 150 nm and up to andincluding 450 nm.

As used herein, all molecular weights are weight average molecularweights (M_(w)) that can be determined using known procedures andequipment if the values are not already known from the literature. Forexample, M_(w) can be determined using Size Exclusion Chromatography(SEC) and values are reported herein as poly(methyl methacrylate)equivalent weights.

In defining various dimensions of features and nanoparticles, eachdimension “average” is determined from at least 2 measurements of thespecific dimension using appropriate measurement techniques andequipment that would be known to one skilled in the art. For example,the average dry thickness of layers described herein can be determinedfrom the average of at least 2 separate measurements taken of a drylayer, for example, using electron microscopy. Similarly, the averagedry thickness or width of lines, grid lines, or other pattern featuresdescribed herein can be the average of at least 2 separate measurementstaken, for example, using electron microscopy. The “average diameter” ofsilver nanoparticles can be determined by at least two measurementsusing light scattering or electron microscopy, such as transmissionelectron microscopy (“TEM”).

The term “aspect ratio” is used to define the morphology of particlesincluding the silver nanoparticles described herein. The term has thewell understood meaning of the ratio of the largest dimension to thesmallest dimensions of an anisotropic particle such as a platelet orrod. In some embodiments of the present invention, the silvernanoparticles in silver-containing compositions (B) and (D) describedbelow is less than 2, or even less than 1.5 and such particles aregenerally considered to be low aspect ratio or near-spherical inmorphology. In other embodiments, the silver nanoparticles insilver-containing compositions (B) and (D) have an aspect ratio ofgreater than or equal to 2 and have plate-like or platelet morphology.

In many embodiments of substrates and articles described herein, thetransparent substrate and all accompanying layers or features on one orboth supporting sides, are considered transparent meaning that itsintegrated transmittance over the noted visible region of theelectromagnetic spectrum (for example from 410 nm to 700 nm) is 70% ormore, or more likely at least 80% or even 90% or more, as measured forexample using a spectrophotometer and known techniques.

Unless otherwise indicated herein, the term “metallic” refers tomaterials that are single pure metals, metal alloys, metallic oxides,metallic sulfides, and materials containing metallic particles such asmicro-particles, nanoparticles, or grains.

Uses

The compositions, articles, and methods described or claimed hereininclude the use of reactive polymers that can be used to formwater-soluble complexes containing either reducible silver ions orreduced silver nanoparticles. The resulting water-soluble complexes havea variety of applications.

In some embodiments, the water-soluble complexes containing the reactivepolymers can be disposed on various substrates in a uniform or patternedmanner for further chemical reactions such as providing catalytic silvernanoparticles that can then be used to form high resolutionelectrically-conductive metal patterns as described herein. Suchelectrically-conductive metal patterns can be incorporated into variousdevices including but not limited to touch screens or other displaydevices that can be used in numerous industrial, consumer, andcommercial products. Thus, the water-soluble complexes can beincorporated into silver-containing compositions described below whereefficient photopolymerization and metal pattern formation is needed invarious articles or devices.

Touch screen technology can comprise different touch sensorconfigurations including capacitive and resistive touch sensors.Capacitive touch sensors can be used in electronic devices withtouch-sensitive features. These electronic devices can include but arenot limited to, televisions, monitors, and projectors that can beadapted to display images including text, graphics, video images,movies, still images, and presentations. The image devices that can beused for these display devices that can include cathode ray tubes (CRT),projectors, flat panel liquid crystal displays (LCD), light emittingdiode (LED) systems, organic light emitting diode (OLED) systems, plasmasystems, electroluminescent displays (ELD), and field emission displays(FED). For example, the present invention can be used to preparecapacitive touch sensors that can be incorporated into electronicdevices with touch-sensitive features to provide computing devices,computer displays, portable media players including e-readers, mobiletelephones and other communicating devices.

Systems and methods of fabricating flexible and optically complianttouch sensors in a high-volume roll-to-roll manufacturing processwherein micro electrically-conductive features can be created in asingle pass are possible using the present invention. The water-solublesilver-containing compositions can be used in such systems and methodswith multiple printing members (such as flexographic printing members)to form multiple high resolution electrically-conductive images frompredetermined designs of patterns provided in those multiple printingmembers. Multiple patterns can be printed on one or both sides of asubstrate. For example, one predetermined pattern can be printed on oneside of the substrate and a different predetermined pattern can beprinted on the opposing side of the substrate that can be a continuousweb.

In other embodiments, the present invention can be used to providesilver-containing articles that can be used for anti-fouling orantimicrobial purposes in aquatic or marine environments, or in clothingor medical devices.

Reactive Polymers

In general, the reactive polymers useful in the practice of thisinvention have two essential features. They comprise pendant groups thatare capable of crosslinking via [2+2] photocycloaddition (defined below)upon exposure to suitable radiation. In addition, the reactive polymersalso comprise sulfonate or sulfonic acid groups that provide sufficientwater-solubility or water-dispersibility as well as silver complexationproperties. While the reactive polymers can be supplied as aqueous-basedcompositions, they are best used when complexed with either reduciblesilver ions or silver nanoparticles as described below on a substratethat can have a large or small surface, including the outer surfaces ofinorganic or organic particles and then dried. Thus, the reactivepolymers are reducible silver ion or silver metal complexing (asdescribed below), water-soluble, and photocrosslinkable.

The reactive polymers can be either condensation or vinyl polymers aslong as the requisite pendant crosslinkable and water-solubilizingsulfonate or sulfonic acid groups are connected to and arranged alongthe reactive polymer backbone. In most embodiments, the useful reactivepolymers are vinyl polymers derived from appropriately selectedethylenically unsaturated polymerizable monomers using known freeradical solution polymerization techniques and conditions, initiators,surfactants, catalysts, and solvents, all of which would be readilyapparent to one skilled in the art from the teaching provided herein.

(a) Recurring Units Having Sulfonate or Sulfonic Acid Groups:

The reactive polymers used in the present invention comprise recurringunits comprising sulfonic acid or sulfonate groups, or mixtures of bothsulfonic acid and sulfonate groups. Such recurring units can be providedby polymerization of suitable ethylenically unsaturated polymerizablemonomers containing such water-solubilizing groups such as vinylsulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-sulfoethyl methacrylate, 3-sulfopropyl methacrylate,styrene sulfonates, and 3-sulfopropyl acrylate. Partially or fullyneutralized counterparts of such monomers are also often readilyavailable and useful for certain polymer synthetic conditions.

Alternatively, such recurring units can be provided by polymerizingcertain precursor ethylenically unsaturated polymerizable monomers thatcomprise pendant precursor groups that can in turn be reacted to providethe desired pendant sulfonic acid or sulfonate groups. For example, suchmonomers include but are not limited to, hydroxy or amino-containingcompounds such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate,2-aminoethyl methacrylate, and 2-aminoethyl acrylate that can be reactedusing a variety of sulfonating agents to provide the desired pendantsulfonic acid or sulfonate groups.

The recurring units described above having the sulfonic acid orsulfonate groups are present in the reactive polymers in an amount of atleast 1 mol %, or more likely at least 5 mol % and up to and including80 mol % or up to and including 95 mol %, all amounts based on the totalrecurring units in the reactive polymer.

Crosslinkable (b) Recurring Units:

The reactive polymers used in the present invention also compriserecurring units comprising a pendant group capable of crosslinking via[2+2] photocycloaddition when appropriately exposed to suitableradiation. While not limited to the following examples, suchphotosensitive crosslinkable groups can be chosen from one or more ofthe following classes of photosensitive crosslinkable groups, all ofwhich can be connected to a recurring unit backbone that is derived fromsuitable ethylenically unsaturated polymerizable monomers:

(i) a photosensitive —C(═O)—CR═CR¹—Y group wherein R and R¹ areindependently hydrogen or an alkyl group having 1 to 7 carbon atoms, a5- to 6-membered cycloalkyl group, an alkoxy group having 1 to 7 carbonatoms, a phenyl group, or a phenoxy group, and Y is an aryl orheteroaryl group;

(ii) a photosensitive, non-aromatic unsaturated carbocyclic group;

(iii) a photosensitive, aromatic or non-aromatic heterocyclic groupcomprising a carbon-carbon double bond that is conjugated with anelectron withdrawing group;

(iv) a photosensitive non-aromatic unsaturated heterocyclic groupcomprising one or more amide groups that are conjugated with acarbon-carbon double bond, which photosensitive non-aromatic unsaturatedheterocyclic group is linked to the water-soluble backbone at an amidenitrogen atom, or

(v) a photosensitive substituted or unsubstituted 1,2-diarylethylenegroup.

Multiple photosensitive crosslinkable groups can be present from thesame or multiple different classes of the crosslinkable groups (i)through (v).

Upon exposure to suitable radiation having a λ_(max) of at least 150 nmand up to and including 700 nm, or more likely exposure to radiationhaving a λ_(max) of at least 150 nm and up to and including 450 nm, thenoted photosensitive crosslinkable groups are electronically excitedsuch that they can react with other pendant groups in the reactivepolymer to form crosslinks for example as the product ofphotocycloaddition reactions.

The reactive polymers particularly become crosslinked among adjacent orproximate (molecularly near enough for [2+2] photocycloadditioncrosslinking) crosslinkable groups during or after the notedirradiation. Thus, essential crosslinking can be accomplished using thereactive polymer without additional crosslinking agents. However, ifdesired, crosslinking can be further provided using distinct compoundsthat are dispersed as crosslinking agents within the compositions orlayers comprising one or more reactive polymers. Such crosslinkingagents react at either the crosslinkable groups or at other pendantgroups such as carboxylic acid groups depending upon the chemicalstructure of crosslinking agent. For the pendant crosslinkable groupsdescribed herein, crosslinking is achieved by having at least two ofsuch crosslinkable groups in proximity that can react with one another.

The crosslinkable [2+2] photocycloaddition groups incorporated into thereactive polymers can absorb photoexposing radiation as described aboveto form an electronically excited state that can undergo pericyclic ringformation to form stable covalent crosslinks. These crosslinks betweenthe polymer chains cause the reactive polymer to become water-insoluble,although the water-insoluble reacted polymer can still absorb andtransport water, ions, or other small molecules. The photoexposingradiation can be followed by additional curing or heating procedures(described below) to allow the excited [2+2] photocycloaddition groupsto properly align with non-excited [2+2] photocycloaddition groups toform additional crosslinks. Curing can be shorted with highertemperatures.

The crosslinked, water-insoluble complex containing the crosslinked,water-insoluble reacted polymer can be crosslinked at a level thatimparts water-insolubility and adhesion to a substrate, but still allowsrapid diffusion of water, metal ions, and other small molecules. Thistype of water-compatible composition is sometimes referred to as ahydrogel. The diffusivity of the complex of crosslinked reacted polymercontaining either reducible silver ions or silver nanoparticles can becontrolled by the designing the level of crosslinking and the additionof hydrophobic recurring units such as the (c) and (d) recurring unitsdescribed below.

The recurring units comprising the noted photosensitive crosslinkable[2+2] photocycloaddition groups can be present in the reactive polymersin an amount of at least 5 mol % or typically at least 5 mol % and up toand including 50 mol %, or even at least 10 mol % and up to andincluding 30 mol %, all amounts based on the total recurring units inthe reactive polymer.

In the (i) class of pendant photosensitive, crosslinkable groups thatcan be present in recurring units arranged along the reactive polymerbackbone can comprise —C(═O)—CR═CR¹—Y groups wherein R, R¹, and Y aredefined as follows.

Specifically, R and R′ can be independently hydrogen or substituted orunsubstituted alkyl groups having at least 1 to 7 carbon atoms(including substituted or unsubstituted methyl, ethyl, isopropyl,t-butyl, hexyl, and benzyl groups, and others that would be readilyapparent to one skilled in the art), substituted or unsubstitutedcycloalkyl group having 5 or 6 carbon atoms in the ring (such ascyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others that would bereadily apparent to one skilled in the art), substituted orunsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups,and others that would be readily apparent to one skilled in the art),substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms(such as methoxy, ethoxy, benzoxy, and others readily apparent to oneskilled in the art), or substituted or unsubstituted phenoxy groups(such as phenoxy, 2,4-dimethylphenoxy, and others that would be readilyapparent to one skilled in the art). In some embodiments, R and R¹ canalso be nitro, cyano, or halogen groups.

More particularly, R and R¹ can be independently hydrogen or substitutedor unsubstituted methyl, ethyl or phenyl groups, especially when Y is asubstituted or unsubstituted phenyl group as described below.

Y can be a substituted or unsubstituted carbocyclic aryl group, or asubstituted or unsubstituted heteroaryl group having one or moreheteroatoms (oxygen, sulfur, or nitrogen) and sufficient carbon atoms tocomplete an aromatic heterocyclic ring. Such aromatic rings can have oneor more substituents that do not adversely affect the desired behaviorin the crosslinking reactions induced by the irradiation describedherein.

Useful Y groups can be either heterocyclic or carbocyclic rings havingdesired aromaticity and any of these rings can be substituted with oneor more substituents that do not adversely affect the function of thereactive polymer. Representative aromatic Y groups include but are notlimited to, substituted or unsubstituted phenyl, naphthyl, anthracyl,4-nitrophenyl, 2,4-dichlorophenyl, 4-ethylphenyl, tolyl,4-dodecylphenyl, 2-nitro-3-chlorophenyl, 4-methoxyphenyl, 2-furyl,2-thienyl, 3-indolyl, and 3-pyridyl rings. The substituted orunsubstituted phenyl rings are particularly useful including but notlimited to phenyl, tolyl, xylyl, 4-methoxyphenyl, hydroxyphenyl, andchlorophenyl groups. Substituted or unsubstituted phenyl or 3-pyridylgroups are particularly useful Y groups.

The pendant groups comprising the crosslinkable and photosensitive—C(═O)—CR═CR¹—Y groups are therefore connected to the reactive polymerbackbone by means of a single connecting bond or a linking group (R²) asdescribed below.

In particular, the essential recurring units comprising the notedcrosslinkable groups can be derived from any ethylenically unsaturatedpolymerizable monomer having appropriate pendant groups comprising oneor more crosslinkable —C(═O)—CR═CR¹—Y groups wherein R, R¹, and Y are asdefined above.

More particularly, such recurring units can be further defined inreference to the following Structure (-A_(i)-) comprising crosslinkablegroups:

In Structure (-A_(i)-), R, R¹, and Y are as defined above. R² can be adivalent linking group including but are not limited to, substituted orunsubstituted alkylene (including haloalkylenes and cyanoalkylenes),alkyleneoxy, alkoxyalkylene, iminoalkylene, cycloalkylene, aralkylene,cycloalkylene-alkylene, and aryloxyalkylene groups wherein the divalenthydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear,branched, or cyclic form). A skilled worker in polymer chemistry wouldbe able to design other useful linking groups using suitable number ofcarbon and hetero (oxygen, nitrogen, or sulfur) atoms in an order andarrangement that are chemically possible. Particularly useful R²divalent groups are substituted or unsubstituted alkylene groups such assubstituted or unsubstituted ethylene or propylenes.

R³, R⁴, and R⁵ can be independently hydrogen, a halogen, a substitutedor unsubstituted alkyl group having 1 to 6 carbon atoms, a substitutedor unsubstituted cyclohexyl group, or a substituted or unsubstitutedphenyl group. In particular, R³, R⁴, and R⁵ can be independentlyhydrogen, chloro, methyl, or ethyl groups.

Some particularly useful ethylenically unsaturated polymerizablemonomers from which -A_(i)- recurring units can be derived include:

2-cinnamoyl-ethyl methacrylate,

2-cinnamoyl-ethyl acrylate, and

2-[3-(3-pyridyl)acryloyl]ethyl methacrylate.

The -A_(i)- recurring units can also be formed after formation of awater-soluble precursor reactive polymer having precursor -A_(i)-recurring units. For example, a water-soluble precursor reactive polymercan be prepared with recurring units derived from vinyl alcohols oracrylate monomers having pendant hydroxyl groups, and the pendanthydroxyl groups can be reacted with cinnamoyl chloride (or similarsubstituted cinnamoyl-like chloride reactants) to form the desired-A_(i)- (or similar) recurring units with pendant water-solubilizingsulfonic acid or sulfonate groups already present before the reaction toform the -A_(i)-recurring units.

(ii) Another class of useful photosensitive crosslinkable groupsarranged along the reactive polymer backbone can comprise pendantphotosensitive (crosslinkable), non-aromatic unsaturated carbocyclicgroups including but not limited to, cyclopropene groups, cyclobutenegroups, cyclopentadiene groups, cyclohexene groups, cyclohexadienegroups, cycloheptene groups, cycloheptadiene groups, cycloheptatrienegroups, cyclooctene groups, indene groups, dihydronaphthalene groups,and norbornene groups. Any of these photosensitive groups can besubstituted with one or more substituents that will not interfere withthe desired properties of the reactive polymer. Where appropriate, suchnon-aromatic unsaturated carbocyclic groups can also contain one or morecarbon-containing fused rings. The cyclopropene groups including theunsaturated cyclopropene groups can be particularly useful.

In general, such useful recurring units can be represented by thefollowing Structure (-A_(ii)-):

Specifically, R, R¹, and R² in Structure (-A_(ii)-) can be independentlyhydrogen or substituted or unsubstituted alkyl groups having at least 1to 7 carbon atoms (including substituted or unsubstituted methyl, ethyl,isopropyl, t-butyl, hexyl, and benzyl groups, and others that would bereadily apparent to one skilled in the art), substituted orunsubstituted cycloalkyl group having 5 or 6 carbon atoms in the ring(such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others thatwould be readily apparent to one skilled in the art), substituted orunsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups,and others that would be readily apparent to one skilled in the art),substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms(such as methoxy, ethoxy, benzoxy, and others readily apparent to oneskilled in the art), or substituted or unsubstituted phenoxy groups(such as phenoxy, 2,4-dimethylphenoxy, and others that would be readilyapparent to one skilled in the art). In some embodiments, R and R¹ canalso be nitro, cyano, or halogen groups.

More particularly, R, R¹, and R² in Structure (-A_(ii)-) can beindependently hydrogen or substituted or unsubstituted methyl, ethyl orphenyl groups, and more particularly, each of these groups is hydrogenor methyl.

E can be a divalent linking group including but not limited to,substituted or unsubstituted alkylene (including haloalkylenes andcyanoalkylenes), alkyleneoxy, alkoxyalkylene, iminoalkylene,cycloalkylene, aralkylene, cycloalkylene-alkylene, aryloxyalkylenegroups wherein the divalent hydrocarbon groups can comprise 1 to 20carbon atoms (in either linear, branched, or cyclic form), carbonyloxy,oxycarbonyl, amido, keto, carbonate, carbamate, and urea. A skilledworker in polymer chemistry would be able to design other useful linkinggroups using suitable number of carbon and hetero (oxygen, nitrogen, orsulfur) atoms in an order and arrangement that are chemically possible.Particularly useful E divalent groups are substituted or unsubstitutedalkylene groups such as substituted or unsubstituted ethylene orpropylenes, or oxycarbonyl.

In Structure (-A_(ii)-), D₁ can represent the carbon atoms necessary tocomplete a three-membered to seven-membered non-aromatic unsaturatedcarbocyclic group (or ring), or particularly the carbon atoms necessaryto complete a non-aromatic, unsaturated 3-membered to 7-memberedcarbocyclic group (or ring) such as a cyclopropene ring, a cyclobutenering, a cyclopentene ring, a cyclohexene ring, or a cycloheptene ring.D₁ can also represent the saturated or unsaturated carbon atoms toprovide an indene or dihydronaphthalene group, or polycyclic rings suchas a norbornene group.

Moreover, in Structure (-A_(ii)-), R³ can be hydrogen, a substituted orunsubstituted alkyl group having 1 to 12 carbon atoms (such as methyl,ethyl, isopropyl, amyl, hexyl, nonyl, decyl, and dodecyl), or asubstituted or unsubstituted aryl group having 6 or 10 carbon atoms inthe ring. Such groups can be substituted with one or more hydroxy,halogen, carbonyl, cyano, alkyl, or alkoxy groups.

In Structure (-A_(ii)-), m can represent the molar amounts of therecurring units that would satisfy the amounts described above for thewater-soluble polymer.

Some particularly useful recurring units of this type represented by thefollowing Structure (-A_(ii2)-) or (-A_(ii3)-):

wherein R, R¹, R², R³, and E are as defined above for Structure(-A_(i)-).

Some useful recurring units of this type can be derived from:

-   2-cyclopropene-1-carboxylic acid, 2,3-diphenyl-,    2-[(2-methyl-1-oxo-2-propen-1-yl)oxy]ethyl ester;-   2-cyclopropene-1-carboxylic acid, 2,3-diphenyl-,    2-[(2-methyl-1-oxo-2-propen-1-yl)amino]ethyl ester;-   4-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) styrene;-   4-(2,3-diphenyl-2-cyclopropene-1-carbonylamino) styrene; and-   4-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy)ethane.

These recurring units can be derived from suitable ethylenicallyunsaturated polymerizable monomers that can then be polymerized undersuitable conditions to provide useful reactive polymers.

Yet another class (iii) of photosensitive crosslinking groups in thereactive polymers comprise pendant photosensitive (crosslinkable),aromatic or non-aromatic heterocyclic groups, each of which comprises acarbon-carbon double bond (>C═C<) that is conjugated with one or moreelectron withdrawing groups. In many embodiments, the carbon-carbondouble bond is conjugated with one or two of the same or differentelectron withdrawing groups, and in most embodiments, the carbon-carbondouble bond is conjugated with only one electron withdrawing group.

It is to be understood that the pendant photosensitive, aromatic ornon-aromatic heterocyclic groups can be single ring groups formed ofcarbon and hetero atoms (such as nitrogen, sulfur, and oxygen), or theycan be fused ring groups with two or more fused rings formed from carbonand suitable heteroatoms.

Useful electron withdrawing groups that can be conjugated with thecarbon-carbon double bond would be readily apparent to one skilled inthe art as the term “electron withdrawing” in reference to a chemicalgroup is well known in the art. However, it is particularly useful whensuch electron withdrawing groups include but are not limited to,carbonyl, ester, thioester, amide, imine, amidine, ether, thioether, andamine groups (or moieties). More generally, the photosensitive(crosslinkable) aromatic or non-aromatic heterocyclic group can be acyclic group that comprises an α,β-unsaturated ketone, α,β-unsaturatedlactone, α,β-unsaturated lactam, α,β-unsaturated ether, α,β-unsaturatedthioether, or α,β-unsaturated amine group. Of these types ofphotosensitive (crosslinkable) aromatic or non-aromatic heterocyclicgroups, those containing a carbonyl group are particularly useful.

For example, the reactive polymers can comprise pendant photosensitive,aromatic or non-aromatic heterocyclic groups selected from the groupconsisting of coumarin, thiocoumarin, quinone, benzoquinone,naphthoquinone, pyran, thiopyran, benzopyran, benzothiopyran, pyranone,thiopyranone, pyridinone, quinoline, and quinolinone groups. Of thesephotosensitive aromatic or non-aromatic heterocyclic groups, pendantphotosensitive coumarin or quinolinone groups are useful and the pendantphotosensitive coumarin groups are most useful because they can bereadily prepared.

Any of the photosensitive aromatic or non-aromatic heterocyclic groupscan be substituted with one or more substituents that will not interferewith the desired properties of the reactive polymer.

In general, useful recurring units can be represented by the followingStructure (-A_(iii)-):

Specifically, in Structure (-A_(iii)-), R, R¹, and R² can beindependently hydrogen or substituted or unsubstituted alkyl groupshaving at least 1 to 7 carbon atoms (including substituted orunsubstituted methyl, ethyl, isopropyl, t-butyl, hexyl, and benzylgroups, and others that would be readily apparent to one skilled in theart), substituted or unsubstituted cycloalkyl group having 5 or 6 carbonatoms in the ring (such as cyclopentyl, cyclohexyl, 4-methylcyclohexyl,and others that would be readily apparent to one skilled in the art),substituted or unsubstituted phenyl groups (such as phenyl, tolyl, andxylyl groups, and others that would be readily apparent to one skilledin the art), substituted or unsubstituted alkoxy groups having 1 to 7carbon atoms (such as methoxy, ethoxy, benzoxy, and others readilyapparent to one skilled in the art), or substituted or unsubstitutedphenoxy groups (such as phenoxy, 2,4-dimethylphenoxy, and others thatwould be readily apparent to one skilled in the art). In someembodiments, R and R¹ can also be nitro, cyano, or halogen groups.

More particularly, R, R¹, and R² can be independently hydrogen orsubstituted or unsubstituted methyl, ethyl or phenyl groups, and moreparticularly, each of these groups can be hydrogen or methyl.

E in Structure (-A_(iii)-) can be a single bond or divalent linkinggroup that can be connected to a carbon atom within D₁. Thus, while Eappears to be connected directly to D₁, E can be connected to any carbonrepresented by D₁. For example, E can be a divalent linking groupincluding but not limited to, substituted or unsubstituted alkylene(including haloalkylenes and cyanoalkylenes), alkyleneoxy,alkoxyalkylene, iminoalkylene, cycloalkylene, aralkylene,cycloalkylene-alkylene, aryloxyalkylene groups wherein the divalenthydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear,branched, or cyclic form), carbonyloxy, oxycarbonyl, amido, keto,carbonate, carbamate, and urea. A skilled worker in polymer chemistrywould be able to design other useful linking groups using suitablenumber of carbon and hetero (oxygen, nitrogen, or sulfur) atoms in anorder and arrangement that are chemically possible. Particularly usefulE divalent groups are substituted or unsubstituted alkylene groups suchas substituted or unsubstituted ethylene or propylenes or oxycarbonyl.

In Structure (-A_(iii)-), D₁ represents the carbon and hetero (sulfur,oxygen, or nitrogen particularly) atoms necessary to complete athree-membered to fourteen-membered aromatic or non-aromaticheterocyclic group (or ring) that includes the carbon-carbon double bondshown in Structure (-A_(iii)-). However, it is essential that either D₁or at least one of the R³ groups (defined below) comprises at least one(and optionally more) electron withdrawing groups that are conjugatedwith the carbon-carbon double bond shown in Structure (-A_(iii)-).

D₁ can also represent the saturated or unsaturated carbon or heteroatoms to provide one or more fused rings such as naphthoquinone,benzopyran, benzothiopyran, benzopyran-2-one (coumarin), quinoline, andquinolinone polyrings. Other useful D₁ ring systems optionallycomprising at least one electron withdrawing group that is conjugatedwith the carbon-carbon double bond would be readily apparent to oneskilled in the art.

Moreover, in Structure (-A_(iii)-), R³ is hydrogen, a substituted orunsubstituted alkyl group having 1 to 12 carbon atoms (such as methyl,ethyl, isopropyl, amyl, hexyl, nonyl, decyl, and dodecyl), a substitutedor unsubstituted aryl group having 6 or 10 carbon atoms in the ring, asubstituted or unsubstituted alkoxy group having 1 to 12 carbon atoms(such as methoxy, 2-ethoxy, t-butoxy, and n-hexoxy), substituted orunsubstituted aryloxy group having 6 or 10 carbon atoms in the ring(such as phenoxy and naphthoxy), cyano, halo, or carbonyl-containinggroup. Such carbonyl-containing groups include but are not limited to,aldehyde, ketone, carboxylic acid, ester, and amide groups. Suchcarbonyl-containing groups can be conjugated with the carbon-carbondouble bond in Structure (-A_(iii))-.

In Structure (-A_(iii)-), m can represent the molar amounts of the notedrecurring units as described above for the reactive polymers.

Some useful recurring units of this type can be derived from

-   7-(2-methacryloyloxyethoxy)-4-methylcoumarin,-   7-(2-methacryloyloxyethoxy)-coumarin,-   7-(3-methacryloyloxysulfopropyl)-4-methylcoumarin,-   7-(methacryloyloxy)-4-methylcoumarin,-   6-(methacryloyloxy)-4-methylcoumarin,-   6-(2-methacryloyloxyethoxy)-4-methylcoumarin,-   7-(2-methacryloyloxyethoxy)-quinoline-2-one,-   7-(2-methacryloyloxyethoxy)-4-methylquinoline-2-one, and-   5-(2-methacryloyloxyethoxy)-naphthoquinone.

The useful recurring units can be derived from suitable ethylenicallyunsaturated polymerizable monomers that can then be polymerized undersuitable conditions to provide useful reactive polymers.

Yet another class (iv) comprises pendant photosensitive (crosslinkable),non-aromatic unsaturated heterocyclic groups, each of which non-aromaticunsaturated heterocyclic groups can comprise one or more amide groups[>N—C(═O)—], and each of the amide groups is arranged in theheterocyclic group (ring) in conjugation with a carbon-carbon doublebond (>C═C<). In many embodiments, such heterocyclic groups have onlyone or two amide groups and the carbon-carbon double bond is conjugatedwith the one or two amide groups arranged within the non-aromaticunsaturated heterocyclic group (ring). In most embodiments, thecarbon-carbon double bond is conjugated with the only one amide group inthe non-aromatic unsaturated heterocyclic group (ring).

It is to be understood that the pendant photosensitive, non-aromaticunsaturated heterocyclic groups can be single ring groups formed ofcarbon and hetero atoms (such as nitrogen, sulfur, and oxygen), or theycan be fused ring groups with two or more fused rings formed from carbonand suitable heteroatoms. In most embodiments, the photosensitive,non-aromatic unsaturated heterocyclic groups are single ring groupshaving 5 to 7 carbon and heteroatoms (usually nitrogen atoms) formingthe ring. At least one, and likely two of the carbon atoms in the ringsalso form carbonyl (>C═O) groups.

Particularly useful reactive polymers can comprise pendantphotosensitive, non-aromatic unsaturated heterocyclic groups selectedfrom the group consisting of substituted or unsubstituted maleimide andthymine groups. Of these photosensitive non-aromatic unsaturatedheterocyclic groups, the substituted maleimide groups are most usefulbecause they can be readily prepared.

Any of the photosensitive non-aromatic unsaturated heterocyclic groupscan be substituted with one or more substituents that will not interferewith the desired properties of the reactive polymer and the reactionsnecessary for crosslinking.

In general, useful recurring units can be represented by the followingStructure (-A_(iv)-):

In Structure (-A_(iv)-), R, R′, and R″ can be independently hydrogen orsubstituted or unsubstituted alkyl groups having at least 1 to 7 carbonatoms (including substituted or unsubstituted methyl, ethyl, isopropyl,t-butyl, hexyl, and benzyl groups, and others that would be readilyapparent to one skilled in the art), substituted or unsubstitutedcycloalkyl group having 5 or 6 carbon atoms in the ring (such ascyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others that would bereadily apparent to one skilled in the art), substituted orunsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups,and others that would be readily apparent to one skilled in the art),substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms(such as methoxy, ethoxy, benzoxy, and others readily apparent to oneskilled in the art), or substituted or unsubstituted phenoxy groups(such as phenoxy, 2,4-dimethylphenoxy, and others that would be readilyapparent to one skilled in the art). In some embodiments, R, R′, and R″can also be nitro, cyano, or halogen groups.

More particularly, R, R′, and R″ can be independently hydrogen orsubstituted or unsubstituted methyl, ethyl or phenyl groups, and moreparticularly, each of these groups can be hydrogen or methyl.

In Structure (-A_(iv)-), L can be a single bond or divalent linkinggroup that can be connected to a nitrogen atom (as shown) within thephotosensitive non-aromatic unsaturated heterocyclic group. For example,L can be a divalent hydrocarbon or aliphatic linking group thatgenerally include 1 to 10 carbon, nitrogen, or oxygen atoms in the chainand can include but not limited to, substituted or unsubstitutedalkylene (including haloalkylenes and cyanoalkylenes); alkyleneoxy;alkoxyalkylene; iminoalkylene; cycloalkylene; aralkylene;cycloalkylene-alkylene; or aryloxyalkylene groups wherein the divalenthydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear,branched, or cyclic form) and can be connected or interrupted withheteroatom-containing groups such as oxy, carbonyl, carbonyloxy,oxycarbonyl, amino, amido, carbonate, carbamate, and urea, or anycombination thereof. A skilled worker in polymer chemistry would be ableto design other useful linking groups using suitable number of carbonand hetero (oxygen, nitrogen, or sulfur) atoms in an order andarrangement that are chemically possible. Particularly useful L divalentgroups are substituted or unsubstituted alkylene groups such assubstituted or unsubstituted methylene, ethylene, or a propylene (anyisomer), or such groups can be used in combination with an oxycarbonyl(such as from an acrylic acid ester group).

In Structure (-A_(iv)-), X represents the 1 to 3 carbon and heteroatoms(usually nitrogen atoms), which in combination with the remaining shownnitrogen and carbon atoms, complete a five- to seven-memberedphotosensitive non-aromatic unsaturated heterocyclic ring. In mostembodiments, X represents at least one carbon atom (for example, acarbonyl carbon atom), or at least one carbon atom (for example, acarbonyl carbon atom) and at least one nitrogen atom such that theresulting amide group is conjugated with the shown carbon-carbon doublebond.

In Structure (-A_(iv)-), R¹ and R² are independently hydrogen or asubstituted or unsubstituted alkyl group having 1 to 10 carbon atoms(such as substituted or unsubstituted methyl, ethyl, isopropyl, amyl,hexyl, nonyl, and decyl groups), or a substituted or unsubstitutedcycloalkyl group having 5 or 6 carbon atoms in the unsaturatedcarbocyclic ring (such as substituted cyclohexyl groups). R¹ and R² arelikely to be the same group such as hydrogen, or unsubstituted methyl orunsubstituted ethyl groups.

Some particular useful representations of such recurring units are shownin the following Structures (-A_(iv1)-), (-A_(iv2)-), and (-A_(iv3)-)

wherein R, R′, R″, L, R¹, and R² are as defined above in Structure(-A_(iv)-) and m is defined below.

Moreover, in Structures (-A_(iv2)-) and (-A_(iv3)-), R³ and R⁴ areindependently hydrogen, or substituted or unsubstituted alkyl groups orsubstituted or substituted cycloalkyl groups for example as used todefine R¹ and R² shown above.

It should be understood that a reactive polymer used in this inventioncan comprise a variety of different photosensitive non-aromaticunsaturated heterocyclic groups in recurring units. For example, thereactive polymer can have recurring units represented by both Structures(-A_(iv1)-) and either (-A_(iv2)-) or (-A_(iv3)-). Alternatively, thereactive polymer can have recurring units represented by both Structures(-A_(iv2)-) and (-A_(iv3)-). Still again, the reactive polymer can haverecurring units represented by all of Structure (-A_(iv1)-),(-A_(iv2)-), and (-A_(iv3)-).

Still another class (v) of useful photosensitive and crosslinkablependant groups comprises photosensitive substituted or unsubstituted1,2-diarylethylene groups. Such groups can be generally represented as—Ar₁-ethylene-Ar₂ wherein Ar₁ is a divalent, substituted orunsubstituted heterocyclic or carbocyclic aromatic group and Ar₂ is amonovalent, substituted or unsubstituted heterocyclic or carbocyclicaromatic group.

For example, some useful reactive polymers comprise pendant groupscomprising photosensitive substituted or unsubstituted 1,2-diarylethylene groups selected from stilbene, styrylnaphthalene,styrylpyridine, styrylpyridinium, styrylquinoline, styrylquinolinium,styrylthiazole, styrylthiazolium, naphthrylphenyl(naphthylene-ethylene-phenyl), naphthrylpyridinium, naphthylthiazolium,1-pyridyl-2-thiazolylethylene, and 1,2-pyridiylethylene groups. Thependant groups comprising photosensitive stilbene, styrylpyridinium,styrylquinoline, or styrylthiazolium groups are particularly useful.

Any of the photosensitive 1,2-diarylethylene groups can be substitutedwith one or more substituents that will not interfere with the desiredproperties of the reactive polymer and the reactions necessary forcrosslinking.

In general, such useful recurring units can be represented by thefollowing Structure (-A_(v)-) showing both reactive polymer backbone andpendant groups attached thereto:

In Structure (-A_(v)-), R, R′, and R″ can be independently hydrogen orsubstituted or unsubstituted alkyl groups having at least 1 to 7 carbonatoms (including substituted or unsubstituted methyl, ethyl, isopropyl,t-butyl, hexyl, and benzyl groups, and others that would be readilyapparent to one skilled in the art), substituted or unsubstitutedcycloalkyl group having 5 or 6 carbon atoms in the ring (such ascyclopentyl, cyclohexyl, 4-methylcyclohexyl, and others that would bereadily apparent to one skilled in the art), substituted orunsubstituted phenyl groups (such as phenyl, tolyl, and xylyl groups,and others that would be readily apparent to one skilled in the art),substituted or unsubstituted alkoxy groups having 1 to 7 carbon atoms(such as methoxy, ethoxy, benzoxy, and others readily apparent to oneskilled in the art), or substituted or unsubstituted phenoxy groups(such as phenoxy, 2,4-dimethylphenoxy, and others that would be readilyapparent to one skilled in the art). In some embodiments, R, R′, and R″can also be nitro, cyano, or halogen groups.

More particularly, R, R′ and R″ can be independently hydrogen orsubstituted or unsubstituted methyl, ethyl or phenyl groups, and moreparticularly, each of these groups can be hydrogen or substituted orunsubstituted methyl groups.

In Structure (-A_(v)-), L can be a single bond or divalent linking groupthat can be connected to a nitrogen atom (as shown) within thephotosensitive non-aromatic unsaturated heterocyclic group. For example,L can be a divalent hydrocarbon or aliphatic linking group thatgenerally include 1 to 10 carbon, nitrogen, or oxygen atoms in the chainand can include but not limited to, substituted or unsubstitutedalkylene (including haloalkylenes and cyanoalkylenes); alkyleneoxy;alkoxyalkylene; iminoalkylene; cycloalkylene; aralkylene;cycloalkylene-alkylene; or aryloxyalkylene groups wherein the divalenthydrocarbon groups can comprise 1 to 20 carbon atoms (in either linear,branched, or cyclic form) and can be connected or interrupted withheteroatom-containing groups such as oxy, carbonyl, carbonyloxy,oxycarbonyl, amino, amido, carbonate, carbamate, and urea, or anycombination thereof. A skilled worker in polymer chemistry would be ableto design other useful linking groups using suitable number of carbonand hetero (oxygen, nitrogen, or sulfur) atoms in an order andarrangement that are chemically possible. Particularly useful L divalentgroups can be substituted or unsubstituted alkylene groups such assubstituted or unsubstituted methylene, ethylene, or a propylene (anyisomer), or such groups can be used in combination with an oxycarbonyl(such as from an acrylic acid ester group), and aliphatic groupscomprising a carbonyloxy group directly attached to the reactive polymerbackbone.

Moreover, in Structure (-A_(v)-), Ar₁ is a divalent carbocyclic orheterocyclic aromatic group that can be substituted or unsubstituted.For example, Ar₁ can be substituted or unsubstituted phenylene,substituted or unsubstituted naphthylene, substituted or unsubstitutedpyridinylene, substituted or unsubstituted quinolinylene, substituted orunsubstituted thiazolylene, substituted or unsubstituted pyridinium,substituted or unsubstituted quinolinium, or substituted orunsubstituted thiazolium. As would be understood by one skilled in theart, some of the useful Ar₁ groups can be quaternary aromatic ringswherein a nitrogen atom in the aromatic ring is optionally attached to Lor is quaternized in a suitable manner, and suitable counterions can bepresent such as a trifluoromethylsulfonate counterion. When the Ar₁rings are substituted, the one or more substituents can be any moietythat will not adversely affect the photosensitivity of the pendant groupor any other properties intended for the reactive polymer. For example,useful substituents can include but are not limited to methyl groups andethyl groups. Particularly useful Ar₂ groups are substituted orunsubstituted phenylene and pyridinium groups.

Ar₂ can be a substituted or unsubstituted carbocyclic or heterocyclicaromatic group as defined for Ar₁ except that Ar₂ is monovalent as shownin Structure (-A_(v)-). Particularly useful Are groups are substitutedor unsubstituted phenyl, substituted or unsubstituted naphthalene,substituted or unsubstituted pyridine, substituted or unsubstitutedpyridinium, substituted or unsubstituted quinoline, substituted orunsubstituted quinolinium, substituted or unsubstituted thiazole, andsubstituted or unsubstituted thiazolium groups, with substituted orunsubstituted phenyl, substituted or unsubstituted pyridinium,substituted or unsubstituted quinolinium groups, and substituted orunsubstituted thiazolium groups being particularly useful. Similarly toAr₁, some of the Ar₂ aromatic rings can be quaternary aromatic ringshaving a positive nitrogen atom, and a suitable counterion, such astrifluoromethylsulfonate, is then present. A skilled worker in the artwould readily know about other suitable counterions.

Moreover, In Structure (-A_(v)-), R¹ and R² are independently hydrogenor substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms(such as substituted or unsubstituted methyl, ethyl, isopropyl, amyl,hexyl, nonyl, and decyl groups), or substituted or unsubstitutedcycloalkyl groups having 5 or 6 carbon atoms in the unsaturatedcarbocyclic ring (such as substituted cyclohexyl groups). R¹ and R² arelikely to be the same group such as hydrogen, or unsubstituted methyl orunsubstituted ethyl groups.

In some embodiments, the reactive polymer comprises recurring unitsrepresented by the following Structure (-A_(v1)-) also showing reactivepolymer backbone to which pendant groups are attached:

wherein R, R′, R″ are as defined above and are particularly hydrogen ormethyl, L is as described above and particularly comprises a carbonyloxygroup directly attached to the backbone, R¹ and R² can be independentlyhydrogen, methyl, or ethyl, R³ can be a suitable substituted orunsubstituted alkyl, substituted or unsubstituted cycloalkyl, orsubstituted or unsubstituted aryl group, X⁻ can be a suitable counterionas described above, and m is as defined below.

In Structures (-A_(v)-) and (-A_(v1)-), m can represent the molaramounts of the recurring units as described above for the reactivepolymers.

Some useful recurring units of this class can be derived from:

-   1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]pyridinium    trifluoromethylsulfonate;-   1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]quinolinium    trifluoromethylsulfonate;-   1-methyl-2-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]thiazolium    trifluoromethylsulfonate;-   4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]pyridine;    and-   1-phenyl-2-[(4-(2-methacryloxyethyl)-carbonyloxyphenyl)]ethylene.

Such useful recurring units can be derived from suitable ethylenicallyunsaturated polymerizable monomers that can then be polymerized undersuitable conditions to provide useful reactive polymers. More likely,such monomers are prepared by attaching a 1,2-diarylethylene group to apolymerizable acrylic group through a linking group by formation of anester, amide or ether bond. For example 4-formylbenzoic acid can beeasily condensed with 4-methylpyridine to form a styrylpyridine groupwith a carboxylic acid functionality suitable for attachment to alinking group on an acrylic monomer such as 2-hydroxyethylmethacrylate.The carboxylic acid and the hydroxyethyl groups can then be attached bya variety of ester forming reactions well known in the art including theknown Mitsunobu reaction.

Optional (c) and (d) Recurring Units:

The reactive polymers used in the present invention can optionallycomprise at least 1 mol % and up to and including 93 mol %, or typicallyat least 10 mol % and up to and including 70 mol %, of (c) recurringunits comprising pendant amide, hydroxyl, lactam, phosphonic acid (orphosphonate), or carboxylic acid (or carboxylate) groups, all based onthe total amount of recurring units in the reactive polymer. Recurringunits comprising pendant hydroxyl, amide, or carboxylic acid groups areparticularly useful. It is also useful to have (c) recurring units thatcomprise multiple different pendant groups from the noted list ofpendant groups.

Useful pendant precursor groups include but are not limited to,anhydrides, alcohols, amines, lactam, lactone, amide, and ester groupsthat can be used to provide the various groups noted above for the (c)recurring units.

For example, useful (c) recurring units can be represented by thefollowing Structure (-C-):

wherein B′ represents a pendant amide, hydroxy, lactam, phosphonic acid,or carboxylic acid group or precursor groups that can be appropriatelyconverted, which group can be directly attached to the reactive polymerbackbone or it can be attached through a suitable divalent linkinggroup.

For example, some useful ethylenically unsaturated polymerizablemonomers from which the (c) recurring units can be derived include butare not limited to, (meth)acrylic acid, itaconic acid, maleic anhydride,fumaric acid, citraconic acid, vinyl benzoic acid, 2-carboxyethylacrylate, 2-carboxyethyl methacrylate, (meth)acrylamide, N-vinylpyrrolidone, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate,vinyl phosphonic acid, N-isopropyl acrylamide, and dimethyl acrylamide.

In addition to the (a), (b), and (c) recurring units described above,the reactive polymers can optionally comprise one or more additionalrecurring units that are different from all (a), (b), and (c) recurringunits, and herein identified as optional (d) recurring units, in anamount of less than 50 mol %, based on the total recurring units in thereactive polymer. Alternatively, (d) recurring units can be present with(a) and (b) recurring units but (c) recurring units are absent.

A skilled polymer chemist would understand how to choose such additional(d) recurring units, and for example, they can be derived from one ormore ethylenically unsaturated polymerizable monomers selected from thegroup consisting of alkyl acrylates, alkyl methacrylates, styrene andstyrene derivatives, vinyl ethers, vinyl benzoates, vinylidene halides,vinyl halides, vinyl imides, and other materials that a skilled workerin the art would understand could provide desirable properties to thereactive polymer. Such (d) recurring units can be represented byStructure (-D-) as follows:

wherein the pendant D groups in Structure (-D-) can be for example,hydrogen, substituted or unsubstituted alkyl groups, substituted orunsubstituted aryl groups, alkyl ester groups, aryl ester groups,halogens, or ether groups.

In addition, some (d) recurring units can comprise an epoxy (such as aglycidyl group) or epithiopropyl group derived for example from glycidylmethacrylate or glycidyl acrylate.

In the recurring units described above, R, R′, and R″ can be the same ordifferent hydrogen, methyl, ethyl, or chloro groups and each type ofrecurring unit can have the same or different R, R′, and R″ groups alongthe reactive polymer backbone. In most embodiments, R, R′, and R″ arehydrogen or methyl, and R, R′, and R″ can be the same or different forthe various (a), (b), (c), and (d) recurring units in a given reactivepolymer.

In the Structures shown above, “m”, “n”, and “p” are used to representthe respective molar amounts of recurring units, based on the totalrecurring units in a given reactive polymer, so that the sum of m, n,and p equal 100 mol % in a given reactive polymer.

The mol % amounts of the various recurring units defined herein for thereactive polymers defined herein are meant to refer to the actual molaramounts present in the reactive polymers. It is understood by oneskilled in the art that the actual mol % values may differ from thosetheoretically possible from the amount of ethylenically unsaturatedpolymerizable monomers that are used in the polymerization reactionsolution. However, under most polymerization conditions that allow highpolymer yield and optimal reaction of all monomers, the actual mol % ofeach monomer is generally within ±15 mol % of the theoretical amounts.

Some representative reactive polymer embodiments include but are notlimited to, the following copolymers and terpolymers wherein the molarratios are theoretical (nominal) amounts based on the actual molar ratioof ethylenically unsaturated polymerizable monomers used in thepolymerization process. The actual molar amounts of recurring units candiffer from the theoretical (nominal) amounts of monomers if thepolymerization reactions are not carried out to completion.

-   Poly(3-sulfopropyl methacrylate potassium salt-co-2-cinnamoyl-ethyl    methacrylate) (80:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-2-cinnamoyl-ethyl    methacrylate) (70:30 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-2-cinnamoyl-ethyl    methacrylate) (50:50 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (30:50:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (5:75:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (5:85:10 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (5:90:5 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (2:78:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methyl    methacrylate-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-butyl    methacrylate-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-styrene-co-2-cinnamoyl-ethyl    methacrylate) (70:10:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic acid-co-butyl    methacrylate-co-2-cinnamoyl-ethyl methacrylate) (10:60:10:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-styrene-co-2-cinnamoyl-ethyl methacrylate) (10:65:5:20 mol    %);-   Poly(3-sulfopropyl methacrylate potassium    salt-co-acrylamide-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol    %);-   Poly(3-sulfopropyl methacrylate potassium    salt-co-acrylamide-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol    %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-2-hydroxyethyl    metacrylate-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-2-hydroxyethyl    metacrylate-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-maleic    anhydride-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-maleic    anhydride-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium    salt-co-N-vinyl-2-pyrrolidone-co-2-cinnamoyl-ethyl methacrylate)    (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-vinyl phosphonic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic    acid-co-2-cinnamoyl-ethyl methacrylate) (80:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic    acid-co-acrylamide-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol    %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic acid-co-2-hydroxyethyl    methacrylate-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic acid-co-maleic    anhydride-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic    acid-co-N-vinyl-2-pyrrolidone-co-2-cinnamoyl-ethyl methacrylate)    (50:30:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic acid-co-vinyl phosphonic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   Poly(styrene sulfonic acid sodium salt-co-2-cinnamoylethyl    methacrylate) (80:20 mol %);-   Poly(styrene sulfonic acid sodium salt-co-methacrylic    acid-co-2-cinnamoylethyl methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl acrylate sodium salt-co-methacrylic    acid-co-2-cinnamoylethyl methacrylate) (50:30:20 mol %);-   Poly(2-sulfoethyl methacrylate sodium salt-co-methacrylic    acid-co-2-cinnamoylethyl methacrylate) (50:30:20 mol %);-   Poly(4-sulfobutyl methacrylate sodium salt-co-methacrylic    acid-co-2-cinnamoylethyl methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium    salt-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (30:50:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (10:70:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-acrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium    salt-co-acrylamide-co-7-(2-methacryloxyethoxy)-4-methylcoumarin)    (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-2-hydroxyethyl    methacrylate-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20    mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-maleic    anhydride-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20    mol %);-   Poly(3-sulfopropyl methacrylate potassium    salt-co-N-vinyl-2-pyrrolidone-co-7-(2-methacryloxyethoxy)-4-methylcoumarin)    (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium salt-co-vinyl phosphonic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate potassium    salt-co-N-vinyl-2-pyrrolidone-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (20:30:30:20 mol    %);-   Poly(styrene sulfonic acid sodium    salt-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);-   Poly(styrene sulfonic acid sodium salt-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);-   Poly(2-acylamide-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-N-(2-(methacryloxy)ethyl)    dimethylmaleimide-) (80:20 mol %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide-) (50:30:20 mol    %);-   Poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide-) (10:70:20 mol    %);-   Poly(styrene sulfonic acid sodium salt-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide-) (50:30:20 mol    %);-   Poly (2-acylamide-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide-) (50:30:20 mol    %);-   Poly [3-sulfopropyl    methacrylate-co-3N-(2-(methacryloxy)ethylthymine] (80:20 mol %);-   Poly [3-sulfopropyl methacrylate-co-methacrylic    acid-co-3N-(2-(methacryloxy)ethyl-thymine] (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate sodium salt-co-methacrylic    acid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethyl    methacrylate) (50:30:20 mol %);-   Poly(3-sulfopropyl methacrylate sodium salt-co-methacrylic    acid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethyl    methacrylate) (10:70:20 mol %);-   Poly(2-acrylamido-2-methyl-1-propanesulfonic acid -co-methacrylic    acid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethyl    methacrylate) (10:70:20 mol %);-   Poly(styrene sulfonic acid sodium salt-co-methacrylic    acid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethyl    methacrylate) (10:70:20 mol %);-   Poly[3-sulfopropyl    methacrylate-co-1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]pyridinium    trifluoromethylsulfonate] (80:20 mol %);-   Poly[3-sulfopropyl methacrylate-co-methacrylic    acid-co-1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]pyridinium    trifluoromethylsulfonate] (10:70:20 mol %);-   Poly[3-sulfopropyl methacrylate-co-methacrylic    acid-co-1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]quinolinium    trifluoromethylsulfonate] (30:50:20 mol %);-   Poly[3-sulfopropyl methacrylate-co-methacrylic    acid-co-1-methyl-2-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]thiazolium    trifluoromethylsulfonate-co-methacrylic acid] (20:60:20 mol %);-   Poly[styrene sulfonic acid-co-methacrylic    acid-co-1-methyl-4-[2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]pyridine]    (50:30:20 mol %); and-   Poly[styrene sulfonic acid sodium    salt-co-2-(4-(2-methacryloxyethyl)-carbonyloxyphenyl)ethenyl]phenyl]    (80:20 mol %).

The reactive polymers useful in the invention generally have a molecularweight (M_(w)) of at least 20,000 and up to and including 1,000,000 asmeasured by gel permeation chromatography (GPC) or by size exclusionchromatography (SEC).

Preparation of the reactive polymers useful in the use of the presentinvention can be accomplished by free radical initiated polymerizationin the appropriate reaction solvent combination. The proper choice ofreaction solvents is desirable for successful polymerization because ofthe wide disparity in polarity between the various ethylenicallyunsaturated polymerizable monomers with the ethylenically unsaturatedpolymerizable monomers providing the (a) recurring units being verypolar or negatively charged and water soluble and the ethylenicallyunsaturated polymerizable monomers that provide (b) recurring unitsbeing relatively non-polar and hydrophobic. It is typical to require upto three reaction solvents in combination to facilitate awell-controlled polymerization. Useful reaction solvents include but arenot limited to, water, ketones such as methyl ethyl ketone, aproticpolar solvents such as N,N-dimethylacetamide, and alcohols such asisopropyl alcohol. Readily available free radical initiators such as2,2′-azodi(2-methylbutyronitrile) (AMBN) or azobis(isobutyronitrile)(AIBN) generally work well in these preparations of the reactionpolymers. The polymerization reaction is typically carried out at 60° C.to 75° C. for about 18 hours. Controlled or living radicalpolymerization methods (see for example, Qui et al., Progress in PolymerScience 26 (2001) 2083-2134) that can produce very narrow molecularweight distributions and highly controlled block copolymers could alsobe used.

Purification of useful reactive polymers is best accomplished bydialysis because of their high water solubility. Additional water can beadded to the completed reaction mixture that is then placed in adialysis bag with a typical retention of polymer chains with an M_(w) of3500 Daltons or more. The dialysis bag containing the crude reactivepolymer is placed in a water washing bath for 1 to 2 days or longer ifneeded. After dialysis, the dilute reactive polymer solution can beconcentrated by evaporation to about 10 to 20 weight % solids which issuitable for storage and dilution to desired coating concentrations.

Silver-Containing Compositions

The reactive polymers described herein can be incorporated into varioussilver-containing compositions described below. Such silver-containingcompositions can be incorporated into the various articles describedbelow or used in various methods as described below.

Each silver-containing composition described herein has only oneessential component, that is, one or more reactive polymers (orcrosslinked reacted polymers) as described above that are complexed witheither reducible silver ions or reduced silver nanoparticles. Thereactive polymers can be used to form crosslinked reacted polymers(rendered water-insoluble) upon exposure to radiation having λ_(max) ofat least 150 nm and up to and including 700 nm, or of at least 250 nmand up to and including 450 nm, as described below. While various otheroptional components can be included as described below, only the complexof reactive polymer and either reducible silver ions or silvernanoparticles is essential for providing the desired uses, articles, andmethods.

Several embodiments of silver-containing compositions are provided foruse in the present invention.

Silver-Containing Composition (A):

In one embodiment, a water-soluble, silver-containing compositioncomprises a water-soluble complex of a reactive polymer (as describedabove) with reducible silver ions. Such a silver-containing compositioncan also be considered a “silver precursor” composition that eventuallycan be used to provide silver metal (nanoparticles) within a polymericcomplex.

One or more complexes of reactive polymers and reducible silver ions asdescribed herein are generally present in silver-containing composition(A) (and in a resulting dry layer) in an amount of at least 10 weight %and up to and including 100 weight %, or typically at least 50 weight %and up to and including 100 weight %, based on the total solids insilver-containing composition (A).

The water-soluble complexes of silver ions (non-reduced silver) andreactive polymers for silver-containing composition (A) can be preparedby adding a highly soluble silver salt such as silver nitrate or silveracetate to an aqueous solution of a reactive polymer with stirring andfor example, using controlled addition rates. The reducible silver ionswill tend to bind with the sulfonate or sulfonic acid groups andoptional carboxylic acid or carboxylate sites in the reactive polymerforming a silver-containing polymer complex or salt that is less solubleand more stable than the original nitrate salt but is still soluble inwater. This unreduced form of the silver polymer complex is nearlycolorless, and can be coated onto a suitable substrate and hardened orpatterned using ultraviolet radiation. The silver ions in the uncoatedsolution or coatings can be reduced to form silver nanoparticles bycontact (such as immersion) with a reducing agent as described below, orsimply by exposure to UV or visible radiation and heat that can causepoor long-term stability. Oxidants such as iodate salts can be added tothe formulation to reduce or eliminate the formation of reduced silverdue to ambient light and heat. The spontaneous formation of silvernanoparticles using a reducing agent is observable because of theappearance of the strong yellow-orange color due to the surface plasmonresonance of the reduced silver nanoparticles in the resultingwater-insoluble complex.

Silver-Containing Composition (B):

In another embodiment, a water-soluble silver-containing compositioncomprises a water-soluble complex of a reactive polymer (as describedabove) with silver nanoparticles. Such silver-containing compositionscan be readily obtained, for example, by reducing the reducible silverions in a silver-containing composition (A) described above. Forexample, this water-soluble composition can be obtained, for example, byreducing the silver ions in water-soluble, silver-containing composition(A) described above.

One or more complexes of reactive polymers and silver nanoparticles asdescribed herein are generally present in silver-containing composition(B) (and in a resulting dry layer) in an amount of at least 10 weight %and up to and including 100 weight %, or typically at least 50 weight %and up to and including 100 weight %, based on the total solids insilver-containing composition (B).

As noted above, the water-soluble complexes of silver nanoparticles andreactive polymers for silver-containing composition (B) can be preparedby reducing the silver ions in silver-containing composition (A)containing the same reactive polymer. For example, starting withsilver-containing composition (A), the rapid formation of a complex ofreactive polymer and silver nanoparticles is easily accomplished by thecareful addition of a silver ion reducing agent such as dimethylamineborane (DMAB) that is especially well suited to work at the inherent lowpH of the polymer solutions. Other silver ion reducing agents areborohydrides (for example, sodium borohydride), hydrazine, hypophosphite(such as sodium hypophosphite), amines (such astetramethylethylenediamine), aldehydes, and sugars can be used for thispurpose if the pH of the composition is properly adjusted. Depending onthe composition of the reactive polymer and formulation conditions,silver nanoparticles having an average diameter of at least 2 nm and upto and including 500 nm, or at least 5 nm and up to and including 300 nmcan be formed and stably dispersed and complexed within the reactivepolymer such that they can be filtered without removing the silvernanoparticles and the silver-containing composition (B) can be coatedwithout forming particulate defects. The resulting complex of reactivepolymer and silver nanoparticles can be strongly colored, especially forsmall particles with a narrow size distribution due to the strongsurface plasmon resonance effect. The complex of reactive polymer andsilver nanoparticles can again be dialyzed if necessary to remove anyreaction products or salts produced as by-products during the formationof the complexes.

Alternatively, silver-containing composition (B) can be prepared bymixing silver nanoparticles from any commercial source in an aqueoussolution of a reactive polymer with stirring until complexation occurs.The silver nanoparticles will tend to bind with the sulfonate orsulfonic acid groups and optional carboxylic acid or carboxylate sitesin the reactive polymer forming a silver nanoparticle-polymer complex.

Silver-Containing Composition (C):

Yet another useful embodiment comprises a crosslinked water-insolublesilver-containing composition of a crosslinked reacted polymer withreducible silver ions. Such crosslinked reacted polymer can be derivedfrom suitable photoexposure of a reactive polymer (as described above)that is complexed with reducible silver ions. Such silver-containingcomposition can be obtained, for example, by photoexposure ofwater-soluble, silver-containing composition (A) described above butbefore any appreciable silver ion reduction occurs. Alternatively, onecan crosslink a reactive polymer as described herein and then imbibe ordiffuse silver ions into it for complexation with the sulfonic acid andany carboxylic acid groups in the reacted polymer.

Silver-Containing Composition (D):

(D) Still another useful embodiment comprises a crosslinkedsilver-containing composition comprising a crosslinked water-insolublecomplex of a crosslinked reacted polymer with silver nanoparticles. Suchcrosslinked reacted polymer can be derived from photoexposure asdescribed herein of a reactive polymer (as described above) that isalready complexed with silver nanoparticles (from appropriate reductionof reducible silver ions). This crosslinked composition can be derivedfor example, by photoexposure of silver-containing composition (B)described above; by both photoexposure and silver ion reduction, in anyorder, of composition (A) described above; or by silver ion reduction ofsilver-containing composition (C) described above. The resulting silvernanoparticles can have an average diameter of at least 2 nm and up toand including 500 nm, or at least 6 nm and up to and including 300 nmsuch that they can be formed and stably dispersed and complexed withinthe reactive polymer so that they can be filtered without removing thesilver nanoparticles and the silver-containing composition (D) can becoated without forming particulate defects. Alternatively, one candiffuse a non-complexed solution of silver nanoparticles into thecrosslinked reactive polymer where the silver nanoparticles willpreferentially bind or complex with the sulfonic acid, carboxylic acid,or other groups.

Silver-containing compositions (A) through (D) generally do not includeseparate crosslinking agents or crosslinking agent precursors becausethe reactive polymer itself includes sufficient crosslinkable groups(described above). However, as noted above, if present, the (d)recurring units can also include additional crosslinking groups.

While not essential, it is sometimes desirable to enhance thesensitivity of some reactive polymers to longer wavelengths (forexample, at least 250 nm and up to and including 700 nm, or at least 250nm and up to and including 450 nm) by including one or morephotosensitizers including triplet state photosensitizers. A variety ofphotosensitizers are known in the art such as benzothiazole andnaphthothiazole compounds as described in U.S. Pat. No. 2,732,301(Robertson et al.), aromatic ketones as described in U.S. Pat. No.4,507,497 (Reilly, Jr.), and ketocoumarins, as described for example inU.S. Pat. No. 4,147,552 (Specht et al.) and U.S. Pat. No. 5,455,143(Ali), the disclosures of all of which are incorporated herein byreference. Particularly useful photosensitizers for long UV and visiblelight sensitivity include but are not limited to,2-[bis(2-furoyl)methylene]-1-methyl-naphtho[1,2-d]thiazoline,2-benzoylmethylene-1-methyl-β-napthothiazoline,3,3′-carbonylbis(5,7-diethoxycoumarin),3-(7-methoxy-3-coumarinoyl)-1-methylpyridinium fluorosulfate,3-(7-methoxy-3-coumarinoyl)-1-methylpyridinium 4-toluenesulfonic acid,and 3-(7-methoxy-3-coumarinoyl)-1-methylpyridinium tetrafluoroborate.Other useful compounds are described in Columns 6 and 7 of U.S. Pat. No.4,147,552 (noted above) which compound disclosure is incorporated hereinby reference. Thioxanthones are also particularly useful for sensitizingthe type (iv) [2+2] photocycloaddition groups such as dimethylmaleide.

One or more photosensitizers can be present in a particular composition(and resulting dry layer) in an amount of at least 0.1 weight % and upto and including 10 weight %, or more likely at least 0.5 weight % andup to and including 5 weight %, based on the total solids in thesilver-containing composition (or total dry weight of a layer of thesilver-containing composition).

Silver-containing compositions (A) through (D) described herein canindividually and optionally include one or more addenda such asfilm-forming compounds, surfactants, plasticizers, filter dyes,viscosity modifiers, and any other optional components that would bereadily apparent to one skilled in the art, and such addenda can bepresent in amounts that would also be readily apparent to one skilled inthe art.

The essential complexes of reactive polymer and either reducible silverions or silver nanoparticles, and any optional compounds describedabove, are generally dissolved or dispersed in water or a mixture ofwater and water-miscible organic solvents to form a silver-containingcomposition that can be applied to a suitable substrate (describedbelow) in a suitable manner. Useful water-miscible organic solventsinclude but are not limited to, alcohols such as methanol, ethanol, andisopropanol and polyols such as ethylene glycol, propylene glycol, andglycerol. The amounts of the complexes and any optional compounds in theaqueous-based silver-containing compositions can be readily determinedby a skilled artisan for desired use in coating.

Inventive Articles

The reactive polymers and silver-containing compositions described abovecan be used to prepare a variety of articles that can be used forvarious purposes as described above, for example for antimicrobialpurposes as well as for preparing electrically-conductive elements (orarticles).

In all of these articles, a silver-containing composition can bedisposed in a suitable manner onto one or multiple surfaces of asuitable substrate. For example, any of the silver-containingcompositions described above can be applied to a suitable substrateusing any suitable method including but not limited to, spin coating,bead coating, blade coating, curtain coating, or spray coating, from asuitable reservoir to form a polymeric layer. Useful substrates can bechosen for a particular use or method as long as the substrate materialwill not be degraded by the silver-containing composition or anytreatments to which the resulting articles are subjected during themethod of this invention. The silver-containing composition can beapplied multiple times if desired to obtain a thicker coating, and driedbetween each coating or dried only after the last application. Water andany water-miscible organic solvents can be removed from thesilver-containing composition using any suitable drying technique.

In general, the final dry coating of any silver-containing compositioncan have an average dry thickness of at least 10 nm and up to andincluding 1 mm, with a dry thickness of at least 0.1 μm and up to andincluding 100 μm being useful for various uses. Such coatings can beuniformly applied on a substrate surface or applied in a suitablepatternwise fashion as described below.

Useful substrates can be composed of glass, quartz, and ceramics as wellas a wide variety of flexible materials such as cellulosic papers andpolymeric films composed of polyesters including poly(ethyleneterephthalate) and poly(ethylene naphthalate), polycarbonates,polyamides, poly(meth)acrylates, or polyolefins. Useful polymericsubstrates can be formed by casting or extrusion methods. Laminates ofvarious substrate materials can also be put together to form a compositesubstrate. Any of the substrates can be treated to improve adhesionusing for example corona discharge, oxygen plasma, ozone or chemicaltreatments using silane compounds such as aminopropyltriethoxysilane.The substrates can be of any suitable dry thickness including but notlimited to at least 10 μm and up to and including 10 mm, depending uponthe intended use of the resulting articles.

Particularly useful substrates are flexible substrates that are composedof poly(ethylene terephthalate) such as biaxially oriented poly(ethyleneterephthalate) (PET) films. These PET films, ranging in dry thickness ofat least 50 μm and up to and including 200 μm, can also comprise, on atleast one supporting side, a polymeric primer layer (also known as asubbing layer, adhesive layer, or binder layer) that can be added priorto or after film stretching. Such polymeric primer layers can comprisepoly(acrylonitrile-co-vinylidene chloride-co-acrylic acid), poly(methylacrylate-co-vinylidene chloride-co-itaconic acid), poly(glycidylmethacrylate-co-butyl acrylate), or various water-dispersiblepolyesters, water-dispersible polyurethanes, or water-dispersiblepolyacrylics, as well as sub-micrometer silica particles. The drythickness of the primer layer can be at least 0.1 μM and up to andincluding 1 μm.

In many embodiments of the present invention, each of the substrates canhave an integrated transmittance of at least 80%, or at least 90% oreven higher to provide articles that have excellent transparency. Suchhighly transparent substrates can be composed of glass (such as flexibleglass) or polymeric films as described above.

The useful substrates can be in any suitable shape or size. They can bein the form of sheets, films, tubes, particles, or various 3-dimensionalshapes depending upon the intended use. Some particularly usefulsubstrates are in the form of continuous webs that can be unrolled froma stock roll, treated in some manner for example to apply asilver-containing composition followed by other treatments and thenrolled up for shipment or later use in roll-to-roll manufacturingprocesses.

If a substrate is in the form of a sheet or roll, it typically has twoopposing planar surfaces known herein as a “first supporting surface”and an “opposing second supporting surface”. A silver-containingcomposition can be disposed in a suitable manner one or both supportingsides of the substrate such as only on the first supporting side, or thesame or different silver-containing composition (such assilver-containing composition) can be disposed on both the firstsupporting side and the opposing second supporting side of thesubstrate.

In some embodiments, a precursor article can be prepared with asubstrate and having a silver-containing composition [for examplesilver-containing composition (A) as described above] disposed on thesubstrate, for example on one or both supporting surfaces of a sheet orcontinuous web. This silver-containing composition can comprise awater-soluble complex of a reactive polymer (as described above) withreducible silver ions.

In other embodiments, a precursor silver ion-containing article cancomprise a substrate and have disposed thereon (for example, in apatternwise fashion) a water-insoluble (crosslinked) silver-containingcomposition [for example, silver-containing composition (D) as describedabove], comprising a crosslinked water-insoluble complex of acrosslinked reacted polymer with reducible silver ions. Such crosslinkedreacted polymer can be derived by photoexposure of a reactive polymer asdescribed above. Such water-insoluble (crosslinked) silver-containingcomposition can be disposed on only the first supporting side of thesubstrate, but in other embodiments, the same or differentwater-insoluble complex can be disposed on both the first supportingside and the opposing second supporting side of the substrate. It stillother embodiments, the same or different water-insoluble (crosslinked)silver-containing composition is disposed on both the first supportingside and the opposing second supporting side of the substrate in thesame or different patternwise fashion (using means described below).

It is also possible to prepare precursor silver-containing articles thatcomprise a substrate and having disposed thereon a water-solublesilver-containing composition [for example, silver-containingcomposition (B) described above] comprising a water-soluble complex of areactive polymer (described above) with silver nanoparticles. Suchwater-soluble silver-containing composition can be disposed on only thefirst supporting side of the substrate, but in other embodiments, thesame or different water-insoluble complex can be disposed on both thefirst supporting side and the opposing second supporting side of thesubstrate. In still other embodiments, the same or differentwater-soluble complex is disposed on both the first supporting side andthe opposing second supporting side of the substrate in the same ordifferent patternwise fashion (using means described below). Suchprecursor silver-containing articles can also comprise a suitablephotosensitizer (as described above) admixed with the water-solublecomplex.

In still other embodiments, a silver-containing article can comprise asubstrate and having disposed thereon a water-insolublesilver-containing composition [for example, the silver-containingcomposition (C) described above] comprising a crosslinkedwater-insoluble complex of a crosslinked reacted polymer with silvernanoparticles. This crosslinked reacted polymer can be derived fromphotoexposure of a reactive polymer as described above. Suchwater-insoluble (crosslinked) silver-containing composition can bedisposed on only the first supporting side of the substrate, but inother embodiments, the same or different water-insoluble complex can bedisposed on both the first supporting side and the opposing secondsupporting side of the substrate. It still other embodiments, the sameor different water-insoluble (crosslinked) silver-containing compositionis disposed on both the first supporting side and the opposing secondsupporting side of the substrate in the same or different patternwisefashion (using means described below).

As prepared using conditions described in more detail below, thesilver-containing article can further comprise anelectrically-conductive metal that has been electrolessly plated on thesame or different crosslinked water-insoluble complex disposed on boththe first supporting side and the opposing second supporting side of thesubstrate. This electrically-conductive metal is typically electrolesslyplated on the crosslinked water-insoluble complex in which the silvernanoparticles serve as catalyst seed metal particles. For example, theelectrolessly plated metal is typically copper, silver or other metalsthat can be catalyzed by silver nanoparticles.

The crosslinked water-insoluble complex can be disposed on the substratein a patternwise fashion, and the silver-containing article can furthercomprise an electrically-conductive metal that has been electrolesslyplated on the crosslinked water-insoluble complex in the samepatternwise fashion so that only the pattern of the water-insolublecomplex is electrolessly plated.

Methods for Making and Using Articles

The present invention provides various methods for providing articles asdescribed above. For example, precursor articles described above can beprepared by disposing a silver-containing composition on a suitablesubstrate (as described above). The silver-containing compositioncomprises a water-soluble complex of a reactive polymer (as describedabove) with reducible silver ions. The silver-containing composition canbe disposed in any suitable manner as described above, such as by usinga flexographic printing member described below, in a uniform manner(over the entire supportive side or surface of the substrate) or in apatternwise fashion to provide any desired predetermined or randompattern on the supporting side. If the substrate has a planar shape, itwill generally include two supporting sides opposite each other (forexample, a first supportive side and an opposing second supportingside), and the silver-containing composition can be disposed in asuitable manner on one or both supporting sides (patternwise oruniformly).

It may also be possible to use the present invention to provide certainspecifically designed patterns for optimal non-toxic bioadhesion controlso that marine organisms are less likely to foul or adhere to theresulting article in which the reducible silver ions have been reducedto silver nanoparticles. Some of such patterns are sometimes identifiedas Sharklet™ patterns as described in U.S. Patent ApplicationPublication 2010/0226943A1 identified above and the disclosure of whichis incorporated herein by reference.

In other embodiments of the present invention, a method is used toprovide an article comprising silver nanoparticles. This methodcomprises, firstly disposing a silver-containing composition (asdescribed above) onto either or both supporting sides of a suitablesubstrate (as described above). Either immediately before or immediatelyafter disposing the silver-containing composition onto the substrate,the reducible silver ions in the water-soluble complex are reduced(using chemistry described below) to form silver nanoparticles (averagediameter described above, for example at least 2 nm and up to andincluding 500 nm) in the water-soluble complex. For example, thereducible silver ions can be reduced using an aqueous solution ofdimethylborane, a borohydride, a hypophosphite, an amine, an aldehyde,or a sugar.

The resulting article can be stored for later use if desired, but inmany embodiments, the water-soluble complex containing the silvernanoparticles is photoexposed using conditions described below (forexample, using ultraviolet radiation having a λ_(max) of at least 150nm) to form a crosslinked, water-insoluble complex comprising the silvernanoparticles on one or both supporting sides of the substrate. Forexample, the water-soluble complex containing the silver nanoparticlescan be photoexposed in a patternwise fashion on either or bothsupporting sides of the substrate. Alternative, the water-solublecomplex containing the silver nanoparticles can be blanketwise(uniformly) photoexposed.

In some embodiments, this method further comprises, after photoexposingthe water-soluble complex to form the crosslinked water-insolublecomplex containing silver nanoparticles,

heating the crosslinked water-insoluble complex containing silvernanoparticles at a temperature sufficient to further crosslink thecrosslinked water-insoluble complex containing the silver nanoparticles.Conditions for this heating treatment are described below.

In addition, after photoexposing the water-soluble complex to form thecrosslinked water-insoluble complex containing silver nanoparticles,

the method can include removing any remaining non-photoexposedwater-soluble complex from the substrate, for example, by washing withwater or another aqueous solution for a sufficient time to remove atleast 90 weight % of the non-photoexposed water-soluble complex.

With or without this removal of non-photoexposed water-soluble complexfrom the substrate, the crosslinked, water-insoluble complex containingsilver nanoparticles, on either or both supporting sides of thesubstrate, can be electrolessly plated using an electrically-conductivemetal using solutions and conditions as described in more detail below.

Thus, in some useful embodiments, the method can comprise:

-   -   patternwise photoexposing the water-soluble complex comprising        silver nanoparticles to form a pattern of crosslinked        water-insoluble complex comprising the silver nanoparticles,

removing any remaining water-soluble complex from the substrate, and

electrolessly plating the pattern of crosslinked water-insoluble complexcomprising the silver nanoparticles using an electrically-conductivemetal.

For example, in such methods, the silver-containing composition can bedisposed on one or both supporting sides of the substrate in apatternwise fashion using a flexographic printing member.

In some particularly useful embodiments, the present invention can beused to prepare electrically-conductive patterns on both sides of aflexible continuous web, such as a continuous (roll) of polymericsubstrate, for example in a roll-to-roll manufacturing operation. Thus,in such embodiments, the method for providing a “dual-sided” article,comprising disposing a silver-containing composition (as describedabove) onto a first supporting side of a suitable substrate (such as acontinuous web). Either immediately before or immediately afterdisposing the silver-containing composition onto the first supportingside of the substrate, the reducible silver ions in the water-solublecomplex can be reduced to form silver nanoparticles in the water-solublecomplex on the first supporting side of the substrate using the reducingconditions and solutions described below. The same or differentsilver-containing composition can then be disposed in a suitable fashiononto an opposing second supporting side of the same substrate. Eitherimmediately before or immediately after disposing the silver-containingcomposition onto the opposing second supporting side of the substrate,the reducible silver ions in the water-soluble complex can be reduced toform silver nanoparticles in the water-soluble complex on the opposingsecond supporting side of the substrate. Following these features, thewater-soluble complex containing the silver nanoparticles on either orboth of the first supporting side and opposing second supporting side ofthe substrate is photoexposed to form a crosslinked water-insolublecomplex comprising the silver nanoparticles on either or both of thefirst supporting side and opposing supporting side of the substrate. Itis also possible to remove any remaining water-soluble complex from boththe first supporting side and the opposing second supporting side of thesubstrate.

In many of such embodiments, the method further comprises:

removing any remaining water-soluble complex from both the firstsupporting side and the opposing second supporting side of the substrate(for example, using a rinse with an aqueous solution), and

electrolessly plating the crosslinked water-insoluble complex on eitheror both of the first supporting side and the second opposing supportingside of the substrate using an electrically-conductive metal (usingelectrolessly plating solutions and conditions described below).

In such embodiments, the method can also comprise:

photoexposing the water-soluble complex containing the silvernanoparticles on either or both of the first supporting side and theopposing second supporting side in a patternwise fashion on thesubstrate.

The photoexposing the water-soluble complex containing the silvernanoparticles on either or both of the first supporting side and theopposing second supporting side of the substrate can be blanketwise(uniformly), or in a patternwise fashion. The photoexposing can becarried out using ultraviolet radiation having a λ_(max) of at least 150nm.

After such features, the method can further comprise, afterphotoexposing the water-soluble complex on either or both of the firstsupporting side and the opposing second supporting side of the substrateto form the crosslinked water-insoluble complex containing silvernanoparticles, and

optionally heating the crosslinked water-insoluble complex containingsilver nanoparticles on either or both of the first supporting side andthe opposing second supporting side of the substrate at a temperaturesufficient to further crosslink the crosslinked water-insoluble complexcontaining the silver nanoparticles. The heating conditions aredescribed in more detailed.

In other embodiments, the method can further comprise, afterphotoexposing the water-soluble complex on either or both of the firstsupporting side and the opposing second supporting side of the substrateto form the crosslinked water-insoluble complex containing silvernanoparticles,

removing any remaining water-soluble complex from both of the firstsupporting side and opposing second supporting sides of the substrate,using water or another aqueous solution.

The reducing feature can be carried out on both supporting sides of thesubstrate using an aqueous solution of dimethylamine borane, aborohydride, a hypophosphite, an amine, an aldehyde, or a sugar.

The following discussion provides some details about representativeelectroless plating methods for use in the present invention.

In electroless plating methods, each aqueous-based “processing”solution, dispersion, or bath (for example, solutions containingelectroless seed metal ions, reducing agent solutions, and solutions forelectroless plating, as well as rinsing solutions) used at variouspoints can be specifically designed with essential components as well asoptional addenda readily apparent to one skilled in the art. Forexample, one or more of those aqueous-based processing solutions caninclude such addenda as surfactants, anti-coagulants, anti-corrosionagents, anti-foamants, buffers, pH modifiers, biocides, fungicides, andpreservatives. The aqueous-based reducing solutions can also includesuitable antioxidants.

Uniform or patternwise exposure can be carried out using radiationhaving a λ_(max) of at least 150 nm and up to and including 700 nm or toradiation having a λ_(max) of at least 250 nm and up to and including450 nm. This exposure can be provided with any suitable exposing sourceor device that provides the desired radiation including but not limitedto, various arc lamps and LED sources. The particular exposing sourcecan be chosen depending upon the absorption characteristics of thecomposition used. The exposing radiation can be projected through lensesand mirrors or through a lens or mask element that can be in physicalcontact or in proximity with a water-soluble complex. Exposure time canrange from a fraction (0.1) of a second and up to and including 10minutes depending upon the intensity of the radiation source and thewater-soluble silver-containing composition. Suitable masks can beobtained by known methods including but not limited to photolithographicmethods, flexographic methods, or vacuum deposition of a chrome maskonto a suitable substrate such as quartz or high quality optical glassfollowed by photolithographic patterning.

It is optional but desirable to heat or bake an article simultaneouslywith or after the exposure but generally before removing thewater-soluble silver-containing composition as described below, at atemperature sufficient to further crosslink the at least partiallycrosslinked water-soluble polymer. In most embodiments, this heating iscarried out at least after the patternwise exposure, but it can becarried out both during and after the patternwise exposure. Such heatingcan be accomplished on a hot plate with vacuum suction to hold thearticle in close contact with the heating surface. Alternatively, theheating device can be a convection oven. The duration of the heatingprocedure is generally less than 10 minutes with heating for least 10seconds and up to and including 5 minutes being most likely. The optimalheating time and temperature can be readily determined with routineexperimentation.

After the imagewise exposure and optional heating procedures, thewater-insoluble complex comprising the reactive polymer and eitherreducible silver ions or silver nanoparticles can be removed from thesubstrate so that there is essentially none (less than 20%, andparticularly less than 10%, by weight of the original amount) remainingon the substrate. This can be done by washing, spraying, or immersingthe article in water, aqueous alkaline solution, or another aqueoussolution for a suitable time and temperature to remove most or allwater-soluble complex from the substrate. Contact with the aqueoussolution can be carried out for a suitable time and temperature so thatwater-soluble complex is desirably removed in the non-exposed regionsbut little removal occurs in the exposed regions containing thecrosslinked water-soluble complex. For example, the contact time can beat least 10 seconds and up to and including 10 minutes, and the contacttemperature can be at room temperature (about 20° C.) and up to andincluding 95° C.

Reduction of the reducible silver ions at a suitable time can be done bycontacting the complex containing such silver ions with a suitablereducing agent for the silver ions, for example by immersion within anaqueous-based reducing solution containing one or more reducing agentsfor a suitable time to cause sufficient silver ion reduction to silvernanoparticles. Alternatively, an aqueous-based reducing solutioncomprising the reducing agent can be sprayed or rolled uniformly onto alayer containing the reducible silver ions.

Useful reducing agents include but are not limited to, an organicborane, an aldehyde such as formaldehyde, aldehyde sugar, hydroquinone,or sugar (or polysaccharide) such as ascorbic acid, and metal ions suchas tin(II). These reducing agents can be used individually or incombination, and the total amount in the aqueous-based reducing solutionused for the reducing procedure can be at least 0.01 weight % and up toand including 20 weight % based on the total reducing solution weight.The amount of reducing agent to be used will depend upon the reducingagent to be used and this can be readily optimized using routineexperimentation. The time and temperature for the reduction can also bereadily optimized in the same manner. Generally, the reducingtemperature is at least room temperature (about 20° C.) and up to andincluding 95° C. and the reducing time can be for at least 1 second andup to and including 30 minutes.

For example, some embodiments of the present invention can be carriedout using an immersion bath comprising 1 reducing solution weight % ofan organic borane such as dimethylamine borane (DMAB) at roomtemperature for up to 3 minutes. Longer or shorter times at highertemperatures are possible if needed.

After a reducing procedure, the complex containing the silvernanoparticles can be washed using distilled water or deionized water oranother aqueous-based solution at a suitable temperature for a suitabletime.

The resulting article can be immediately immersed in an aqueous-basedelectroless metal plating bath or solution, or the article can be storedwith just the catalytic pattern comprising the silver nanoparticles aselectroless seed metal particles for use at a later time.

For example, the article containing the silver nanoparticles in thecrosslinked, water-insoluble complex can be contacted with anelectroless plating metal that is the same as or different from theelectroless seed silver nanoparticles. In most embodiments, theelectroless plating metal is a different metal from the electroless seedsilver nanoparticles.

Any metal that will likely electrolessly “plate” on the electroless seedsilver nanoparticles can be used at this point, but in most embodiments,the electroless plating metal can be for example copper(II), silver(I),gold(IV), palladium(II), platinum(II), nickel(II), chromium(II), andcombinations thereof. Copper(II), silver(I), and nickel(II) areparticularly useful electroless plating metals.

The one or more electroless plating metals can be present in theaqueous-based electroless plating bath or solution in an amount of atleast 0.01 weight % and up to and including 20 weight % based on totalsolution weight.

Electroless plating can be carried out using known temperature and timeconditions, as such conditions are well known in various textbooks andscientific literature. It is also known to include various additivessuch as metal complexing agents or stabilizing agents in theaqueous-based electroless plating solutions. Variations in time andtemperature can be used to change the metal electroless platingthickness or the metal electroless plating deposition rate.

A useful aqueous-based electroless plating solution or bath is anelectroless copper(II) plating bath that contains formaldehyde as areducing agent. Ethylenediaminetetraacetic acid (EDTA) or salts thereofcan be present as a copper complexing agent. For example, copperelectroless plating can be carried out at room temperature for severalseconds and up to several hours depending upon the desired depositionrate and plating rate and plating metal thickness.

Other useful aqueous-based electroless plating solutions or bathscomprise silver(I) with EDTA and sodium tartrate, silver(I) with ammoniaand glucose, copper(II) with EDTA and dimethylamineborane, copper(II)with citrate and hypophosphite, nickel(II) with lactic acid, aceticacid, and a hypophosphite, and other industry standard aqueous-basedelectroless baths or solutions such as those described by Mallory et al.in Electroless Plating: Fundamentals and Applications 1990.

After the electroless plating procedure, the resulting product articlecan be removed from the aqueous-based electroless plating bath orsolution and can again be washed using distilled water or deionizedwater or another aqueous-based solution to remove any residualelectroless plating chemistry.

To change the surface of the electroless plated metal for visual ordurability reasons, it is possible that a variety of post-treatments canbe employed including surface plating of still at least another (thirdor more) metal such as nickel or silver on the electrolessly platedmetal (this procedure is sometimes known as “capping”), or the creationof a metal oxide, metal sulfide, or a metal selenide layer that isadequate to change the surface color and scattering properties withoutreducing the conductivity of the electrolessly plated (second) metal.Depending upon the metals used in the various capping procedures of themethod, it may be desirable to treat the electrolessly plated metal witha seed metal catalyst in an aqueous-based seed metal catalyst solutionto facilitate deposition of additional metals.

As one skilled in the art should appreciate, the individual treatmentfeatures or steps described above for these methods can be carried outtwo or more times before proceeding to the next procedure or step. Forexample, multiple treatments with an aqueous-based reducing solution oraqueous-based electroless metal plating solution can be carried out insequence, using the same or different conditions. Sequential washing orrinsing steps can also be carried out where appropriate.

The present invention provides at least the following embodiments andcombinations thereof, but other combinations of features are consideredto be within the present invention as a skilled artisan would appreciatefrom the teaching of this disclosure:

1. A method for providing a silver-containing article, the methodcomprising:

disposing a silver-containing composition onto a first supporting sideof a substrate, the silver-containing composition comprising awater-soluble complex of a reactive polymer with reducible silver ions,the reactive polymer comprising: (a) greater than 1 mol % of recurringunits comprising sulfonic acid or sultanate groups, (b) at least 5 mol %of recurring units comprising a pendant group capable of crosslinkingvia [2+2] photocycloaddition, and optionally (c) at least 1 mol % ofrecurring units comprising a pendant amide, hydroxyl, lactam, phosphonicacid, or carboxylic acid group, all amounts based on the total recurringunits in the reactive polymer.

2. The method of embodiment 1, wherein the reactive polymer comprises atleast 5 mol % of the recurring units comprising sulfonic acid orsultanate groups based on the total amounts of recurring units in thereactive polymer.

3. The method of embodiment 1 or 2, wherein the reactive polymercomprises at least 5 mol % and up to and including 50 mol % of therecurring units comprising a pendant group capable of crosslinking via[2+2] photocycloaddition based on the total recurring units in thereactive polymer.

4. The method of any of embodiments 1 to 3, wherein the reactive polymercomprises at least 1 mol % and up to and including 93 mol % of recurringunits comprising a pendant hydroxyl, amide, or carboxylic acid group,based on the total recurring units in the reactive polymer.

5. The method of any of embodiments 1 to 4, wherein the recurring unitscomprising a pendant group capable of crosslinking via [2+2]photocycloaddition comprise:

(i) a photosensitive —C(═O)—CR═CR¹—Y group wherein R and R′ areindependently hydrogen or an alkyl group having 1 to 7 carbon atoms, a5- to 6-membered cycloalkyl group, an alkoxy group having 1 to 7 carbonatoms, a phenyl group, or a phenoxy group, and Y is an aryl orheteroaryl group;

(ii) a photosensitive, aromatic or non-aromatic unsaturated carbocyclicgroup;

(iii) a photosensitive, non-aromatic heterocyclic group comprising acarbon-carbon double bond that is conjugated with an electronwithdrawing group;

(iv) a photosensitive non-aromatic unsaturated heterocyclic groupcomprising one or more amide groups that are conjugated with acarbon-carbon double bond, which photosensitive non-aromatic unsaturatedheterocyclic group is linked to the water-soluble backbone at an amidenitrogen atom, or

(v) a photosensitive substituted or unsubstituted 1,2-diarylethylenegroup.

6. The method of any of embodiments 1 to 5, wherein the reactive polymeris one of the following:

-   poly(3-sulfopropyl methacrylate potassium salt-co-2-cinnamoyl-ethyl    methacrylate) (80:20 mol %);-   poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (2:78:20 mol %);-   poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (5:75:20 mol %);-   poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %);-   poly(3-sulfopropyl methacrylate-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (30:50:20 mol %);-   poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   poly(3-sulfopropyl methacrylate potassium salt-co-2-hydroxyethyl    methacrylate acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol    %);-   poly(3-sulfopropyl methacrylate potassium    salt-co-acrylamide-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol    %);-   poly(3-sulfopropyl methacrylate potassium    salt-co-N-vinyl-2-pyrrolidone-co-2-cinnamoyl-ethyl methacrylate)    (50:30:20 mal %);-   poly(3-sulfopropyl methacrylate potassium salt-co-maleic    anhydride-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   poly(3-sulfopropyl methacrylate potassium salt-co-vinyl phosphonic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   poly(2-acylamido-2-methyl-1-propanesulfonic    acid-co-2-cinnamoyl-ethyl methacrylate) (80:20 mol %);-   poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %);-   poly(styrene sulfonic acid sodium salt-co-2-cinnamoyl-ethyl    methacrylate) (80:20 mol %);-   poly(styrene sulfonic acid sodium salt-co-methacrylic    acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);-   poly(3-sulfopropyl methacrylate potassium    salt-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);-   poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   poly(3-sulfopropyl methacrylate potassium salt-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (10:70:20 mol %);-   poly(styrene sulfonic acid sodium    salt-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);-   poly(styrene sulfonic acid sodium salt-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   poly(2-acylamido-2-methyl-1-propanesulfonic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);-   poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);-   poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (10:70:20 mol %);-   poly(3-sulfopropyl methacrylate potassium    salt-co-acrylamide-co-7-(2-methacryloxyethoxy)-4-methylcoumarin)    (50:30:20 mol %);-   poly(3-sulfopropyl methacrylate potassium salt-co-2-hydroxyethyl    methacrylate-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20    mol %);-   poly(3-sulfopropyl methacrylate potassium salt-co-maleic    anhydride-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20    mol %);-   poly(3-sulfopropyl methacrylate potassium    salt-co-N-vinyl-2-pyrrolidone-co-7-(2-methacryloxyethoxy)-4-methylcoumarin)    (50:30:20 mol %);-   poly(3-sulfopropyl methacrylate potassium    salt-co-N-vinyl-2-pyrrolidone-co-methacrylic    acid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (20:30:30:20 mol    %);-   poly (3-sulfopropyl methacrylate-co-N-(2-(methacryloxy)ethyl)    dimethylmaleimide) (20:80 mol %);-   poly (3-sulfopropyl methacrylate-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (50:30:20 mol    %);-   poly (3-sulfopropyl methacrylate-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (10:70:20 mol    %);-   poly (styrene sulfonic acid sodium salt-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (50:30:20 mol    %);-   poly (styrene sulfonic acid sodium salt-co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (10:70:20 mol    %);-   poly (2-acylamido-2-methyl-1-propanesulfonic acid -co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (50:30:20 mol    %);-   poly (2-acylamido-2-methyl-1-propanesulfonic acid -co-methacrylic    acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (10:70:20 mol    %);-   poly(3-sulfopropyl methacrylate sodium salt-co-methacrylic    acid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethyl    methacrylate) (10:70:20 mol %);-   poly(styrene sulfonic acid sodium salt-co-methacrylic    acid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethyl    methacrylate) (10:70:20 mol %); and-   poly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-methacrylic    acid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethyl    methacrylate) (10:70:20 mol %).

7. The method of any of embodiments 1 to 6, wherein thesilver-containing composition further comprises a photosensitizer.

8. The method of any of embodiments 1 to 7, wherein the substrate has anintegrated transmittance of at least 90%.

9. The method of any of embodiments 1 to 8, comprising disposing thesilver-containing composition onto a supporting side of the substrate ina patternwise fashion.

10. The method of embodiment 9, comprising disposing thesilver-containing composition onto a supporting side of the substrate ina patternwise fashion using a flexographic printing member.

11. The method of any of embodiments 1 to 8, comprising disposing thesilver-containing composition onto a supporting side of the substrate ina uniform fashion.

12. The method of any of embodiments 1 to 11, further comprising:

either immediately before or immediately after disposing thesilver-containing composition onto the substrate, reducing the reduciblesilver ions in the water-soluble complex to form silver nanoparticles inthe water-soluble complex.

13. The method of embodiment 12, further comprising:

after reducing the reducible silver ions, photoexposing thewater-soluble complex containing the silver nanoparticles to form acrosslinked water-insoluble complex comprising the silver nanoparticles.

14. The method of any of embodiments 1 to 13, comprising:

photoexposing the water-soluble complex containing the silvernanoparticles in a patternwise fashion on the substrate.

15. The method of any of embodiments 1 to 14, comprising:

reducing the silver ions in the water-soluble complex to form silvernanoparticles having an average diameter of at least 2 nm and up to andincluding 500 nm.

16. The method of any of embodiments 14 or 15, further comprising:

after photoexposing the water-soluble complex to form the crosslinkedwater-insoluble complex containing silver nanoparticles,

heating the crosslinked water-insoluble complex containing silvernanoparticles at a temperature sufficient to further crosslink thecrosslinked water-insoluble complex containing the silver nanoparticles.

17. The method of any of embodiments 14 to 16, further comprising, afterphotoexposing the water-soluble complex to form the crosslinkedwater-insoluble complex containing silver nanoparticles,

removing any remaining water-soluble complex from the substrate.

18. The method of any of embodiments 12 to 17, comprising reducing thereducible silver ions in the water-soluble complex using an aqueoussolution of dimethyl borane, a borohydride, a hypophosphite, an amine,an aldehyde, or a sugar.

19. The method of any of embodiments 12 to 18, further comprising:

electrolessly plating the crosslinked water-insoluble complex using anelectrically-conductive metal.

20. The method of any of embodiments 1 to 19, comprising:

-   -   disposing the silver-containing composition onto the first        supporting side of a substrate,

either immediately before or immediately after disposing thesilver-containing composition onto the first supporting side of thesubstrate, reducing the reducible silver ions in the water-solublecomplex to form silver nanoparticles in the water-soluble complex on thefirst supporting side of the substrate,

disposing the same or different silver-containing composition onto anopposing second supporting side of the substrate,

either immediately before or immediately after disposing thesilver-containing composition onto the opposing second supporting sideof the substrate, reducing the reducible silver ions in thewater-soluble complex to form silver nanoparticles in the water-solublecomplex on the opposing second supporting side of the substrate, and

photoexposing the water-soluble complex containing the silvernanoparticles on either or both of the first supporting side andopposing second supporting side of the substrate, to form a crosslinkedwater-insoluble complex comprising the silver nanoparticles on either orboth of the first supporting side and opposing supporting side of thesubstrate, and

optionally, removing any remaining water-soluble complex from both thefirst supporting side and the opposing second supporting side of thesubstrate.

21. The method of embodiment 20 further comprising:

removing any remaining water-soluble complex from both the firstsupporting side and the opposing second supporting side of thesubstrate, and

electrolessly plating the crosslinked water-insoluble complex on eitheror both of the first supporting side and the second opposing supportingside of the substrate using an electrically-conductive metal.

22. The method of embodiment 20 or 21, comprising:

photoexposing the water-soluble complex containing the silvernanoparticles on either or both of the first supporting side and theopposing second supporting side in a patternwise fashion on thesubstrate.

23. The method of any of embodiments 20 to 22, comprising:

-   -   reducing the silver ions in the water-soluble complex on either        or both the first supporting side and the opposing second        supporting side to form silver nanoparticles having an average        diameter of at least 2 nm and up to and including 500 nm.

24. The method of any of embodiments 1 to 23, wherein the substrate is acontinuous web of transparent polymeric film having an integratedtransmittance of at least 80%.

The following Examples are provided to illustrate the practice of thisinvention and are not meant to be limiting in any manner.

Synthesis of 7-(2-Methacryloyloxyethoxy)-4-methylcoumarin

5.44 g of 4-Methylumbelliferone (7-hydroxy-4-methylcoumarin) wassuspended in 150 ml of tetrahydrofuran (THF) and 4.42 g of2-hydroxyethyl methacrylate were added, followed by 8.42 g oftriphenylphosphine. The solids slowly dissolved with stirring at roomtemperature under nitrogen. Then, 6.37 g of diisopropyl azodicarboxylatewere added drop-wise while the temperature was kept below 25° C. Thereaction solution was stirred overnight at room temperature.

Most of the solvent was evaporated and then ether was added toprecipitate a white solid that was put into a freezer for a few hours.The solid was collected by filtration and rinsed with ether, and driedon the filter to obtain 12.14 g of a white solid that was purified bychromatography (silica gel: 50/50 ethyl acetate/methylene chloride).This procedure provided a white solid that was slurried with heptane andfiltered and dried on the filter to provide a total of 6.77 g of thedesired monomer.

Alternative Synthesis of 7-(2-Methacryloyloxyethoxy)-4-methylcoumarinMonomer

15.3 g of 4-methylumbelliferone (7-hydroxy-4-methylcoumarin) wasdissolved in about 300 ml of dimethylacetamide (DMA) in a 3-neck 1 literflask with an overhead stirrer. 48 g of potassium carbonate, 20.8 g of2-((methylsulfonyl)oxy)ethyl methacrylate prepared from 2-hydroxyethylmethacrylate using standard procedures, and 1.66 g of potassium iodidewere then added and the mixture was heated in an oil bath at 70° C.about 18 hours. Thin layer chromatography was used to determine that thereaction was complete. The reaction solution was cooled and poured intoabout 1 liter of water, stirred for about an hour, and the precipitatewas filtered. The precipitate was rinsed with another 1 liter of waterthen heptane and dried on the filter. The desired product was confirmedby NMR. A portion of the product was further purified by silica gelchromatography with ethyl acetate. The ethyl acetate was removed byevaporation and the product was crystallized from heptane to obtain awhite powder.

Synthesis of 2-Cinnamoyl-ethyl Methacrylate Monomer

To a 500 ml, 3 neck round-bottomed flask equipped with a condenser andmagnetic stir bar, 2-hydroxyethyl methacrylate, (11.30 g, 0.0868 mole)(Mw=130.14 g/mole), dichloromethane (DCM) (60 g), and triethylamine(Mw=101.19 g/mole) (8.50 g, 0.084 mole) were added. This solution wasstirred until it was homogenous and then it was placed in an ice bath. Asolution of cinnamoyl chloride (Mw=166.6 g/mole) (13.33 g, 0.080 mole)dissolved in 30 g of DCM was added slowly dropwise over 15 minutes.After this addition, the reaction solution was allowed to come to roomtemperature and then placed in oil bath at 40° C. and refluxed for 60minutes to complete the reaction. The solution was then cooled andremoved from the oil bath and the resulting amine hydrochlorideprecipitate was filtered off. Additional DCM was added and the solutionwas placed in a separatory funnel, the filtered solution was washedtwice with sodium bicarbonate, then twice with distilled water, oncewith dilute hydrochloric acid solution, and then twice with distilledwater. The organic layer was place over magnesium sulfate for 30 minutesand filtered. The DCM was removed and the remaining product was placedunder high vacuum at room temperature overnight to remove any residualDCM. The final product was a clear oil with a yellow tint with an Mw of260.29 g/mole. The product purity was verified by NMR.

Synthesis of 2-(2,3-diphenyl-2-cyclopropene-1-carboxyl)ethylMethacrylate Monomer

Crude 2,3-diphenylcyclopropene-1-carboxylic acid was purified byrecrystallization (hot filtered) using acetone. The carboxylic acid (8.0g, 0.034 moles) was suspended in about 100 ml of dichloromethane in a250 ml single-neck round-bottom flask equipped with a condenser andstirred magnetically under nitrogen. A 2 molar solution (21 ml) ofoxalyl chloride in dichloromethane (5.37 g, 0.042 moles) was addeddropwise at room temperature and then a few drops ofN,N-dimethylformamide were added to help promote the reaction (gasevolution of HCl, CO, and CO₂ began). The reaction solution was stirredat room temperature for about 5 hours while the reaction was monitoredby thin layer chromatography (the solid slowly dissolved whilereacting). The reaction solution became a clear yellow in color when allsolid had dissolved. The solvent(s) was evaporated and the residue wasre-crystallized in hexane with a small amount of ethyl acetate (hotfiltered) in the freezer overnight and 6.90 g (80% yield) of off-whitecrystals of diphenylcyclopropene carboxylic acid chloride werecollected.

The resulting diphenylcyclopropene carboxylic acid chloride (6.90 g,0.027 mole) was dissolved in 30 ml of dichloromethane and the solutionwas added dropwise at room temperature to a solution of 2-hydroxyethylmethacrylate (3.88 g, 0.030 mole) and triethylamine (2.88 g, 0.028 mole)dissolved in 50 ml of dichloromethane in a 250 ml single-neck flask. Theresulting reaction solution was stirred at room temperature undernitrogen overnight. Water was then added to the reaction solution andextracted three times with dichloromethane. The combined organics werewashed twice with water, dried over magnesium sulfate, and evaporated todryness. Methanol was then added to the oil that remained and thesolution was set in a freezer overnight to crystallize after which 6.45g (68%) of beige crystals were collected and another 1.07 g was obtainedfrom the filtrate for a total yield of 7.52 g (80%). The combined solidwas purified by chromatography (silica gel: 95/5dichloromethane/methanol) and 4.35 g (46%) of off-white crystals of theexpected ethylenically unsaturated polymerizable monomer were collectedand kept frozen until used for preparation of a reactive polymer.

Synthesis of N-(2-(methacryloxy)ethyl) dimethylmaleimide Monomer

N-(2-hydroxyethyl)maleimide was prepared in toluene from dimethylmaleicanhydride and ethanolamine using conventional methods.N-(2-hydroxyethyl)maleimide (10.15 g) and 6.68 g of triethylamine weredissolved in 100 ml of dichloromethane (DCM). Methacryloyl chloride (7ml) diluted with DCM was added slowly with stirring to avoid heating.The triethylamine hydrochloride precipitate formed and the reactionsolution was held for an additional 6 hours. The reaction solution waswashed twice with 200 ml aliquots of dilute sodium bicarbonate, then 2additional washings were carried out using distilled water and then thephases were allowed to separate. The DCM phase was dried over anhydrousmagnesium sulfate. The DCM was evaporated to obtain a clear liquidsuitable for polymerization. The expected ethylenically unsaturatedmonomer structure was confirmed by NMR.

COMPARATIVE EXAMPLES Preparation of Comparative Polymer A fromMethacrylic acid and 2-Cinnamoyl-ethyl Methacrylate (80:20 mol % Ratio)

5.17 g of methacrylic acid, 3.90 g of 2-cinnamoyl-ethyl methacrylate,and 0.09 g of AMBN polymerization initiator were weighed out into a 100ml single-neck round bottom flask and suspended in 36.3 g ofN,N-dimethyl acetamide (DMA) and purged with nitrogen for 30 minutes.The flask was capped with a septum and set into a preheated oil bath at75° C. overnight with magnetic stirring. After about 18 hours, thereaction mixture had become clear, colorless, and viscous. It was cooledand the contents of the flask were added to about 500 ml of ethylacetate with overhead stirring. The solid was collected by filtration,dried in a 40° C. oven, redissolved in DMA at about 25 weight % solids,and precipitated again in ethyl acetate. The precipitate was filteredand then dried in a vacuum oven. A 13 weight % aqueous solution wasprepared by neutralizing 50 mol % of the methacrylic acid with a 2weight % sodium hydroxide solution. The weight average molecular weight(M_(w)) of the resulting polymer was 262,000 as determined by sizeexclusion chromatography (SEC).

Preparation of Comparative Polymeric Silver Ion Complex A

A 5.0 g solution of a silver ion complex of Comparative Polymer A(containing no sulfonate groups) was prepared as follows:

3.27 g of the 13 weight % Comparative Polymer A solution was combinedwith 0.71 g of distilled water followed by the addition of 0.614 g of 2molar silver nitrate added slowly with stirring forming a clearsolution. A solid gel formed, demonstrating that a solublepolymer-silver ion complex could not be prepared using ComparativePolymer A.

Preparation of Comparative Polymer B from 3-Sulfopropyl

Methacrylate, Methacrylic acid, and 2-Cinnamoyl-ethyl Methacrylate(1:79:20 mol % Ratio)

2.55 g of methacrylic acid, 0.09 g of 3-sulfopropyl methacrylate, 1.95 gof 2-cinnamoyl-ethyl methacrylate, and 0.046 g of AMBN polymerizationinitiator were weighed out into a 100 ml single-neck round bottom flaskand suspended in a solvent mixture of 6.12 g of water, 6.12 g of methylethyl ketone, and 6.12 g of isopropyl alcohol. The resulting reactionmixture was purged with nitrogen for 30 minutes and the flask was cappedwith a septum and set in a preheated oil bath at 70° C. overnight withmagnetic stirring. The reaction solution was cooled, additional waterwas added, and the contents of the flask were placed in a dialysis bagand dialyzed for 3 days. A gel-like precipitate formed during dialysis.A 2 weight % sodium hydroxide solution was added to neutralize 50 mol %of the available acid groups and a clear solution formed that wasconcentrated to 7.75 weight % solids by evaporation. The weight averagemolecular weight (M_(w)) of the resulting polymer was 567,000 asdetermined by size exclusion chromatography (SEC). The precipitation ofthis polymer during dialysis indicates that the 1 mol % of 3-sulfopropylmethacrylate recurring units was not adequate to maintain the solubilityof the resulting polymer without neutralizing some of the acid groups.

Preparation of Comparative Polymeric Silver Ion Complex B

A 5.0 g solution of the silver ion complex of Comparative Polymer Bcontaining 1 mol % of sulfopropyl recurring units was prepared asfollows:

4.125 g of the 7.76 weight % solution were placed in a vial with amagenta stir bar and 0.463 g of 2 molar silver nitrate were added slowlywith stirring. A very soft clumpy gel was formed, demonstrating that thelevel of sulfonate groups in the polymer was insufficient to form awater-soluble polymer-silver ion complex.

Preparation of Comparative Polymer C Using Methacrylic acid and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (80:20 mol % Ratio)

4.0 g of methacrylic acid, 3.35 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin, and 0.07 g of AMBNpolymerization initiator were weighed out into a 100 ml single-neckround-bottom flask, suspended in 29.68 g of N,N-dimethyl acetamide(DMA), and purged with nitrogen for 30 minutes. The flask was cappedwith a septum and set in a preheated oil bath at 65° C. overnight withmagnetic stirring. After about 18 hours, the reaction solution hadbecome clear, colorless, and viscous. The reaction solution was thencooled and the contents of the flask were added to about 500 ml ofacetone with overhead stirring. The solid was collected by filtration,any large chunks were crushed using a mortar and pestle and thenredissolved in DMA at about 20 weight % solids. The solution wasprecipitated in about 1.6 liters of water and the precipitate wasfiltered and dried in a vacuum oven. About 5.33 g of a white solid wascollected and the desired polymer structure was verified by NMR. Theweight average molecular weight (Mw) of the resulting polymer was231,000 as determined by size exclusion chromatography (SEC). A prepared17.1 weight % solids aqueous solution of the polymer was neutralized at75 mol % using dimethylethanolamine (DMEA).

Preparation of Comparative Polymeric Silver Ion Complex from ComparativePolymer C

A 5.0 g solution of the silver ion complex of Comparative Polymer Cderived from only methacrylic acid and7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomers and nosulfonate-bearing monomer units was prepared as described for the silverion complex Comparative Polymer A. A solid gel formed that demonstratesthat a carboxylate based polymer will not form a soluble silver ioncomplex when the polymer contains recurring units derived from7-(2-methacryloyloxyethoxy)-4-methylcoumarin to provide crosslinking andpatterning capability.

Preparation of Comparative Polymer D Using 3-Sulfopropylmethacrylate andMethacrylic Acid (10:90 mol % Ratio)

1.50 g of 3-sulfopropyl methacrylate was dissolved in 28 g of distilledwater in a 250 ml round bottom flask followed by addition of 4.72 g ofmethacrylic acid and 28 g of isopropyl alcohol and 0.12 g of AMBNinitiator. The reaction mixture was purged with nitrogen for 30 minutes,capped with a septum and set in a preheated oil bath at 70° C. overnightwith magnetic stirring. The reaction mixture was cooled and additionalwater was added and the contents of the flask were placed in a dialysisbag with MWCO of 3500 and dialyzed for about 18 hours. The resultingclear solution was concentrated to 12.41 weight % solids by evaporation.The weight average molecular weight (Mw) of the resulting polymer was294,000 as determined by size exclusion chromatography (SEC).

Preparation of Comparative Polymer E Using 3-Sulfopropyl Methacrylateand Methacrylic Acid (50:50 mol % Ratio)

3.75 g of 3-sulfopropyl methacrylate were dissolved in 23 g of distilledwater in a 250 ml round-bottom flask followed by addition of 1.30 g ofmethacrylic acid, 23 g of isopropyl alcohol, and 0.10 g of AMBNinitiator. The reaction mixture was purged with nitrogen for 30 minutes,capped with a septum, and set in a preheated oil bath at 70° C.overnight with magnetic stirring. The reaction mixture was cooled andadditional water was added and the contents of the flask were placed ina dialysis bag with MWCO of 3500 and dialyzed for about 18 hours. Theresulting clear solution was concentrated to 13.04 weight % solids byevaporation. The weight average molecular weight (M_(w)) of theresulting polymer was 113,000 as determined by size exclusionchromatography (SEC).

Preparation of Comparative Polymeric Silver Ion Complexes fromComparative Polymers D and E

0.49 g of a 2 molar silver nitrate solution was added slowly withstirring to a quantity of each of Comparative Polymers D and E toprepare 8.5 weight % polymer solutions. Clear solutions were formed and0.5 weight % of TERGITOL® 15-S-9 surfactant was added to each clearsolution to aid coating. Each of the resulting solutions was filteredwith a 1 μm glass filter, coated on a substrate, and photoexposed asdescribed below.

Preparation of Comparative Polymeric Silver Nanoparticle Complexes fromComparative Polymers D and E

0.49 g of a 2 molar silver nitrate solution was added slowly withstirring to a quantity of each of Comparative Polymers D and E toprepare 8.5 weight % polymer solutions. To each solution, 0.126 g of a 4weight % dimethylamine borane (DMAB) solution was added with goodstirring. Each solution immediately turned a deep yellow-orange color,indicative of the surface plasmon resonance absorption from silvernanoparticles of approximately 10 to 40 nm in average diameter. Then,0.5 weight % TERGITOL® 15-S-9 surfactant was added to aid coating andeach solution was filtered with a 1 μm glass filter, coated onto asubstrate, and photoexposed as described below.

Coating and Patterning of Comparative Polymers D and E

A coatable formulation of each of Comparative Polymers D and E wasprepared by diluting each Comparative Polymer to 8.5 weight % solidswith distilled water and then 0.5 weight % TERGITOL® 15-S-5 surfactant.Each of the formulations was spin coated at 3000 rpm onto an acryliclayer-subbed poly(ethylene terephthalate) substrate. Samples of eachcoated formulation was allowed to age for 30 minutes, then photoexposedthrough a chrome-on-quartz mask with lines and features down to 1 μmline-width with a broad band UV lamp with a 260 to 320 nm dichroicbandpass filter for various times ranging from 2 to 120 seconds. Samplesof each photoexposed coating was then allowed to age at room temperaturefor about 30 minutes and were then heated for 1 minute on a 60° C.vacuum hotplate. Each aged coating was then immersed in agitateddistilled water bath for 2 minutes to remove the non-exposed polymerfrom the substrate. No pattern was observed on any of the photoexposedcoatings of all formulations because all of the coated polymer, whetherphotoexposed or non-exposed was removed from the substrate during the 2minute distilled water washing, indicating that no significantcrosslinking occurred in these polymers during photoexposure. TheseComparative Examples show that since the Comparative Polymers do notcontain [2+2] photocycloaddition groups such as 2-cinnamoyl-ethylmethacrylate, 7-(2-methacryloyloxyethoxy)-4-methylcoumarin, and othersdescribed above 1.0 cannot form water-insoluble polymeric patterns whenexposed to UV light.

Coating and Patterning of Silver Ion and Silver Nanoparticle Complexesof Comparative Copolymers D and E

The polymeric silver ion and silver nanoparticle complexes describedabove were coated and exposed identically to the polymer-onlyformulations described above. All of the silver-containing polymericcomplexes, whether photoexposed or non-exposed were washed off thesubstrate and did not form any pattern, again indicating that it is anessential requirement that the polymers in the silver-containingcomplexes contain recurring units having crosslinkable pendant groupsthat can undergo [2+2] photocycloaddition upon exposure to UV light.

Preparation of Comparative Polymer F Using Vinyl Phosphonic Acid with7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (80:20 mol % Ratio)

3.0 g of vinyl phosphonic acid, 2.0 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin, and 0.05 g of AMBNinitiator were weighed out in a 100 ml single-neck round-bottom flask,dissolved in 23 g of N—N-dimethylacetamide (DMA), purged with nitrogenfor 30 minutes, capped with a septum, and set in a preheated oil bath at75° C. overnight with magnetic stirring. After about 18 hours, thereaction mixture was clear, colorless, and viscous. The reaction mixturewas cooled and additional water was added and the contents of the flaskwere placed in a dialysis bag with MWCO of 3500 and dialyzed for about18 hours. The resulting polymer precipitated during dialysis. Theprecipitate was filtered and the solid was dried in a vacuum oven. Anattempt was made to solubilize the precipitate by neutralizing thephosphonic acid groups with sodium hydroxide, but the resultingdispersion was unstable and settled out. The weight average molecularweight (Mw) of the polymer was 13,700 as determined by size exclusionchromatography (SEC).

Preparation of Comparative Polymer G Using Vinyl Phosphonic Acid and2-Cinnamoyl-ethyl Methacrylate (80:20 mol % Ratio)

2.16 g of vinyl phosphonic acid was placed in a 100 ml single-neckround-bottom flask with 6.53 g of distilled water, 6.53 g of MEK, and6.53 g of IPA followed by 0.034 g of AMBN initiator and 1.30 g of2-cinnamoyl-ethyl methacrylate. The reaction mixture was then purgedwith nitrogen for 30 minutes, capped with a septum, and set in apreheated oil bath at 70° C. overnight with magnetic stirring. Afterabout 18 hours, the reaction mixture was clear, colorless, and viscous.The reaction mixture was cooled and the contents of the flask wereplaced in a dialysis bag with MWCO of 3500 and dialyzed for about 18hours. The resulting polymer precipitated during dialysis. Theprecipitate was filtered and the solid was dried in a vacuum oven. Theprecipitate was soluble in dimethyl formamide (DMF) but was not solublein a sodium hydroxide solution.

The poor solubility of Comparative Polymers F and G show that phosphonicacid groups do not impart adequate solubility to the polymers andtherefore the pendant sulfonic acid or sulfonate groups described aboveare critical to the formation of stable aqueous solutions of thereactive polymers according to this invention that contain suitablepending crosslinking groups as described above.

Preparation of Comparative Polymer 11 Using Vinyl Phosphonic Acid,Methacrylic Acid, and 7-(2-Methacryloyloxyethoxy)-4-methylcoumarin(50:30:20 mol % Ratio)

2.0 g of vinyl phosphonic acid, 0.96 g of methacrylic acid, 2.13 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin, and 0.05 g of AMBNinitiator were weighed out into a 250 ml single-neck round-bottom flaskand dissolved in 23 g of N—N-dimethyl acetamide (DMA), then purged withnitrogen for 30 minutes, capped with a septum, and set in a preheatedoil bath at 75° C. overnight with magnetic stirring. After about 18hours, the reaction mixture was clear, colorless, and viscous. As thereaction mixture was cooled, the polymer precipitated in water, and wasfiltered and dried in a vacuum oven. An 11% aqueous solution was made byaddition of a 5 weight % sodium hydroxide solution adequate toneutralize the phosphonic acid monomer units. The weight averagemolecular weight (M_(w)) of the resulting polymer was 61,700 asdetermined by size exclusion chromatography (SEC).

Preparation of Comparative Polymer I Using Vinyl Phosphonic Acid,Methacrylic Acid, and 2-Cinnamoyl-Ethyl Methacrylate (50:30:20 Mol %Ratio)

2.7 g of vinyl phosphonic acid, 1.3 g of methacrylic acid, 2.60 g of2-cinnamoylethyl methacrylate, and 0.066 g of AMBN initiator were placedin a 100 ml single-neck round-bottom flask with 8.80 g of distilledwater, 8.80 g of MEK, and 8.80 g of isopropyl alcohol. The reactionsolution was then purged with nitrogen for 30 minutes, capped with aseptum, and set in a preheated oil bath at 70° C. overnight withmagnetic stirring. After about 18 hours, the reaction mixture was clear,colorless, and viscous. The reaction mixture was cooled and the contentsof the flask were placed in a dialysis bag with MWCO of 3500 anddialyzed for about 18 hours. The resulting polymer precipitated duringdialysis. The precipitate was filtered and the solid was dried in avacuum oven. An aqueous solution at 13.5 weight % polymer was preparedby adding enough 45% KOH to neutralize both the pendant methacrylic acidand the phosphonic acid groups. The weight average molecular weight (Mw)of the resulting polymer was 111,000 as determined by size exclusionchromatography (SEC).

Preparation of Comparative Polymeric Silver Ion Complexes fromComparative Polymers H and I

A silver ion complex of each of Comparative Polymers H and I containingrecurring units derived from vinyl phosphonic acid in place of recurringunits derived from sulfonic acid according to the present invention wereprepared as described above for the silver ion complex of ComparativePolymer A. A non-filterable sticky precipitate was formed using each ofComparative Polymers H and I, demonstrating that the pendant phosphonicacid groups, even when combined with pendant neutralized carboxylic acidgroups do not provide water soluble silver ion complexes and thereforecannot be used according to the present invention to provide stablewater-soluble polymeric silver ion complexes.

Preparation of Comparative Polymer J from N-vinyl-2-pyrrolidone and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (80:20 mol % Ratio)

3.0 g of N-vinyl-2-pyrrolidone, 1.95 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin, and 0.05 g of AMBNpolymerization initiator were weighed out into a 100 ml single-neckround bottom flask, suspended in 17 ml of tetrahydrofuran (THF), andpurged with nitrogen for 30 minutes. The flask was capped with a septumand set in a preheated oil bath at 65° C. overnight with magneticstirring. After about 18 hours, the reaction mixture was clear,colorless, and viscous. The reaction mixture was cooled and the contentsof the flask were added to about 500 ml of heptanes to precipitate thepolymer. The polymer was collected by filtration and dried in a vacuumoven. About 4.5 g of solid was collected that was not soluble in water,dichloromethane (DCM), or N,N-dimethylacetamide (DMA).

Preparation of Comparative Polymer K from N-vinyl-2-pyrrolidone,Methacrylic acid, and 7-(2-Methacryloyloxyethoxy)-4-methylcoumarin(50:30:20 mol % Ratio)

2.0 g of N-vinyl-2-pyrrolidone, 0.93 g of methacrylic acid, 2.08 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin, and 0.05 g of AMBNpolymerization initiator were weighed out into a 100 ml single neckround bottom flask, suspended in 17 ml of tetrahydrofuran (THF), andpurged with nitrogen for 30 minutes. The flask was capped with a septumand set in a preheated oil bath at 65° C. overnight with magneticstirring. After about 18 hours the reaction mixture was clear,colorless, and viscous. The reaction solution was cooled and thecontents of the flask were added to about 500 ml of heptane toprecipitate the polymer that was collected by filtration and dried in avacuum oven. The resulting solid was not soluble in water, 20 weight %potassium hydroxide solution, cyclopentanone, ethyl acetate, diethylether, methanol, dichloromethane (DCM), or N,N-dimethylacetamide (DMA).

While poly(vinyl pyrrolidone) polymers such as Comparative Polymers Jand K are generally soluble in water, the presence of crosslinkablerecurring units containing pendant [2+2] photocycloaddition groups willcause the polymers to become insoluble in water. It is thus critical asshown below that the incorporation of pendant sulfonic acid andsulfonate groups in the polymers impart water-solubility and coatabilitywhile the noted crosslinkable groups and silver ions or silvernanoparticles that can dramatically reduce water-solubility of thepolymers.

Preparation of Comparative Polymer L using Acrylamide and2-Cinnamoyl-ethyl methacrylate (80:20 mol % Ratio)

2.16 g of acrylamide, 1.98 g of 2-cinnamoyl-ethyl methacrylate, and0.088 g of AMBN initiator were placed in a 250 ml single-neckround-bottom flask with 12.54 g of distilled water, 12.54 g of MEK, and12.54 g of isopropyl alcohol. The reaction mixture was then purged withnitrogen for 30 minutes, capped with a septum, and set in a preheatedoil bath at 70° C. overnight with magnetic stirring. After about 18hours, the reaction mixture was cloudy. The reaction mixture was cooledand the contents of the flask were placed in a dialysis bag with MWCO of3500 and dialyzed for about 18 hours. The resulting polymer precipitatedduring dialysis and the precipitate was not soluble in water.

Preparation of Comparative Polymer M using Acrylamide, Methacrylic acid,and 2-Cinnamoylethyl Methacrylate (70:10:20 mol % Ratio)

0.32 g of methacrylic acid, 1.87 g of acrylamide, 1.95 g of2-cinnamoylethyl methacrylate, and 0.041 g of AMBN initiator were placedin a 250 ml single-neck round-bottom flask with 7.82 g of distilledwater, 7.82 g of MEK, and 7.82 g of isopropyl alcohol. The reactionmixture was then purged with nitrogen for 30 minutes, capped with aseptum, and set in a preheated oil bath at 70° C. overnight withmagnetic stirring. After about 18 hours, the reaction mixture was clearand viscous. The reaction mixture was cooled and water was added to thecontents causing the polymer to precipitate. Addition of base adequateto neutralize the pendant carboxylic acid groups was not able tosolubilize the polymer.

The water-insolubility of Comparative Polymers L and M demonstrate thatalthough polymers containing recurring units derived from acrylamide aregenerally soluble in water, the presence of the recurring unitscontaining crosslinkable [2+2] photocycloaddition groups as describedabove makes the polymers water-insoluble. Therefore, it is demonstratedbelow that it is essential to include at least some pendant sulfonicacid or sulfonate groups in the polymers to maintain water solubilityand coatability in the presence of both the [2+2] photocycloadditiongroups and the complexed metal ions or metal nanoparticles that all candramatically reduce the water solubility of the polymer.

The following identifiers of ethylenically unsaturated polymerizablemonomers are used below in TABLES I and II.

TABLE I summaries properties of the Comparative Polymers described abovethat are outside the present invention in that they do not contain theessential pendant [2+2] photocycloaddition groups or they contain 1 mol% or less of pendant sulfonic acid or sulfonate groups. Thus, theseComparative Polymers will either not suitably crosslink uponphotoexposure or they will not have suitable water-solubility as apolymer or in the resulting silver ion polymeric complexes. Thus, theycannot be used for coating and patterning as described for the presentinvention.

Water-Soluble Monomers:

Methacrylic Acid (MA)

Acrylamide (AA)

N-vinyl pyrrolidone (VP)

Vinyl phosphonic acid (VPH)

3-Sulfopropyl methacrylate (SPMA)

Styrene sulfonic acid (SS)

2-Acrylamido-2-methyl-1-propanesulfonic acid (AMPS)

2-Hydroxyethyl methacrylate (HEM)

Maleic anhydride (MD)

Monomers with [2+2] Photocycloaddition Groups:

2-Cinnamoyl-ethyl methacrylate (CIN)

7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (COUM)

2-(2,3-Diphenyl-2-cyclopropene-1-carboxyl)-ethyl methacrylate (DPCP)

N-(2-(methacryloxy)ethyl) dimethylmaleimide (DMMI)

TABLE I Summary of Performance for Comparative Polymers Water- Cross-Mon- soluble linkable omer Polymer Polymer Monomer(s) Monomer ratiosProperties Comparative A MA CIN 80:20 Water-insoluble polymeric silverion complex Comparative B SPMA, MA CIN 1:79:20 Water-insoluble polymericsilver ion complex Comparative C MA COUM 80:20 Water-insoluble polymericsilver ion complex Comparative D SPMA, MA none 10:90 Not patternable; nocrosslinking Comparative E SPMA, MA none 50:50 Not patternable; nocrosslinking Comparative F VPH COUM 80:20 Water-insoluble polymerComparative G VPH CIN 80:20 Water-insoluble polymer Comparative H VPH,MA COUM 50:30:20 Water-insoluble polymeric silver ion complexComparative I VPH, MA CIN 50:30:20 Water-insoluble polymeric silver ioncomplex Comparative J VP COUM 80:20 Water-insoluble polymer ComparativeK VP, MA COUM 50:30:20 Water-insoluble polymer Comparative L AA CIN80:20 Water-insoluble polymer Comparative M AA, MA CIN 70:10:20Water-insoluble polymer

Inventive Examples Preparation of Inventive Reactive Polymer a Using3-Sulfopropyl Methacrylate, Methacrylic Acid, and 2-Cinnamoyl-ethylMethacrylate (2:78:20 mol % Ratio)

2.52 g of methacrylic acid, 0.18 g of 3-sulfopropyl methacrylate, 1.95 gof 2-cinnamoyl-ethyl methacrylate, and 0.047 g of AMBN polymerizationinitiator were weighed out into a 100 ml single-neck round-bottom flaskand suspended in a solvent mixture of 6.2 g of water, 6.2 g of methylethyl ketone, and 6.2 g of isopropyl alcohol. The reaction solution waspurged with nitrogen for 30 minutes. The flask was capped with a septumand set into a preheated oil bath at 70° C. overnight with magneticstirring. The reaction solution was then cooled, additional water wasadded, and the contents of the flask were placed in a dialysis bag withMWCO (Molecular Weight Cut Off) of 3500 and dialyzed for about 18 hours.The resulting clear solution was concentrated to 12.99 weight % solidsby evaporation. The weight average molecular weight (Mw) of theresulting Inventive reactive polymer was 1,110,000 as determined by sizeexclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer B Using 3-SulfopropylMethacrylate, Methacrylic Acid, and 2-Cinnamoyl-ethyl Methacrylate(5:75:20 mol % Ratio)

2.42 g of methacrylic acid, 0.46 g of 3-sulfopropyl methacrylate, 1.95 gof 2-cinnamoyl-ethyl methacrylate, and 0.048 g of AMBN polymerizationinitiator were weighed out into a 100 ml single-neck round-bottom flaskand suspended in a solvent mixture of 6.44 g of water, 6.44 g of methylethyl ketone, and 6.44 g of isopropyl alcohol. The reaction solution waspurged with nitrogen for 30 minutes. The flask was capped with a septumand set into a preheated oil bath at 70° C. overnight with magneticstirring. The reaction solution was cooled, additional water was added,and the contents of the flask were placed in a dialysis bag with MWCO of3500 and dialyzed for about 18 hours. The resulting clear solution wasconcentrated to 14.33 weight % solids by evaporation. The weight averagemolecular weight (Mw) of the resulting Inventive reactive polymer was631,000 as determined by size exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer C Using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, and 2-Cinnamoyl-ethylMethacrylate (10:70:20 mol % Ratio)

In a 100 ml single-neck round bottom flask, 0.92 g of 3-sulfopropylmethacrylate potassium salt, 2.26 g of methacrylic acid, 1.95 g of2-cinnamoyl-ethyl methacrylate, and 51 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture of 6.84 g of water, 6.84 gof methyl ethyl ketone (MEK), and 6.84 g of isopropyl alcohol (IPA). Thereaction solution was purged with nitrogen and the flask was capped witha septum and set into a preheated oil bath at 75° C. overnight. Thereaction mixture was then cooled and placed in a dialysis bag with MWCOof 3500 and dialyzed until the bag was fully swollen. The contents werethen evaporated to a concentration of 12.76 weight % solids. The weightaverage molecular weight (Mw) of the resulting Inventive reactivepolymer was 219,000 as determined by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer D from 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, and 2-Cinnamoyl-ethylMethacrylate (30:50:20 mol % Ratio)

In a 100 ml single-neck round bottom flask 2.77 g of 3-sulfopropylmethacrylate potassium salt, 1.61 g of methacrylic acid, 1.95 g of2-cinnamoyl-ethyl methacrylate, and 63 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture consisting of 17.94 g ofwater, 6.10 g of methyl ethyl ketone (MEK), and 11.84 g of isopropylalcohol (IPA). The reaction solution was purged with nitrogen and theflask was capped with a septum and set into a preheated oil bath at 70°C. overnight. The reaction mixture was then cooled and placed in adialysis bag with MWCO of 3500 and dialyzed until the bag was fullyswollen. The contents were then evaporated to a concentration of 19.07weight % solids. The weight average molecular weight (M_(w)) of theresulting Inventive reactive polymer was 180,000 as determined by sizeexclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer E from 3-SulfopropylMethacrylate potassium salt, Methacrylic Acid, and 2-Cinnamoyl-ethylMethacrylate (50:30:20 mol % Ratio)

In a 100 ml single-neck round bottom flask 3.08 g of 3-sulfopropylmethacrylate potassium salt, 0.65 g of methacrylic acid, 1.30 g of2-cinnamoyl-ethyl methacrylate, and 61 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture of 14.25 g of water, 4.85g of methyl ethyl ketone (MEK), and 9.41 g of isopropyl alcohol (IPA).The reaction solution was purged with nitrogen and the flask was cappedwith a septum and set into a preheated oil bath at 70° C. overnight. Thereaction solution was cooled and placed in a dialysis bag with MWCO of3500 and dialyzed until the bag was fully swollen. The contents werethen evaporated to a concentration of 18.9 weight % solids. The weightaverage molecular weight (M_(w)) of the resulting Inventive reactivepolymer was 160,000 as determined by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer F from 3-SulfopropylMethacrylate Potassium Salt and 2-Cinnamoyl-ethyl Methacrylate (80:20mol % Ratio)

4.93 g of 3-sulfopropyl methacrylate potassium salt were dissolved in8.25 g of water in a 100 ml single-neck round bottom flask followed byaddition of 8.25 g of dimethylacetamide (DMA), 8.42 g of isopropylalcohol (IPA), 61 mg of AMBN polymerization initiator, and 1.30 g of2-cinnamoyl-ethyl methacrylate. The resulting reaction solution waspurged with nitrogen and the flask was capped with a septum and set in apreheated oil bath at 75° C. overnight. The reaction solution was cooledand placed in a dialysis bag with MWCO of 3500 and dialyzed until thebag was fully swollen. The contents were then evaporated to aconcentration of 19.8 weight % solids. The average molecular weight (Mw)of the resulting Inventive reactive polymer was determined to be 138,000by size exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer G using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic acid, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (10:70:20 mol % Ratio)

3.65 g of 3-sulfopropyl methacrylate potassium salt, 2.15 g ofmethacrylic acid and 2.88 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomers were weighed outinto a 250 ml single-neck round-bottom flask dissolved in a solventmixture of 14 g water, 14 g of dimethylacetamide (DMA), and 5.3 g ofisopropyl alcohol. 0.09 g of AMBN polymerization initiator was added andnitrogen was bubbled through the slurry for 60 minutes before heating inan oil bath at 65° C. for about 18 hours. The solution reaction wascooled and diluted with water to form a clear solution. The reactionsolution was then dialyzed for about 18 hours and then concentrated to a15.05 weight % solids solution that was suitable for coating. The weightaverage molecular weight (M_(w)) of the resulting Inventive reactivepolymer was 422,000 as determined by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer H Using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (30:50:20 mol % Ratio)

1.43 g of 3-sulfopropyl methacrylate potassium salt, 3.50 g ofmethacrylic acid, and 3.35 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomers were weighed outinto a 100 ml single-neck round-bottom flask dissolved in a solventmixture of 11 g water, 11 g of dimethylacetamide (DMA), and 8.25 g ofisopropyl alcohol. 0.08 g of AMBN polymerization initiator was added andnitrogen was bubbled through the slurry for 30 minutes before heating itin an oil bath at 65° C. for about 18 hours. The reaction solution wascooled and diluted with water to form a clear solution. The reactionsolution was dialyzed for about 60 hours and then concentrated to an11.4 weight % solids solution that was suitable for coating. The weightaverage molecular weight (M_(w)) of the resulting Inventive reactivepolymer was 800,000 as determined by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer I Using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (50:30:20 mol % Ratio)

4.93 g of 3-sulfopropyl methacrylate potassium salt, 1.03 g ofmethacrylic acid, and 2.31 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomers were weighed outin a 250 ml single-neck round-bottom flask dissolved in a solventmixture of 11 g water, 11 g of dimethylacetamide (DMA), and 8.25 g ofisopropyl alcohol. 0.08 g of AMBN polymerization initiator was added andnitrogen was bubbled through the slurry for 60 minutes before heating itin an oil bath at 65° C. for about 18 hours. The reaction solution wascooled and diluted with water to form a clear solution. The reactionsolution was then dialyzed for about 60 hours and then concentrated to a12.17 weight % solids solution that was suitable for coating. The weightaverage molecular weight (Mw) of the resulting Inventive reactivepolymer was 414,000 as determined by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer J from 3-SulfopropylMethacrylate Potassium Salt and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (80:20 mol % Ratio)

10.0 g of 3-sulfopropyl methacrylate potassium salt and 2.93 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin were weighed out into a 250ml single-neck round-bottom flask and dissolved in a solvent mixture of22 g of water, 22 g of dimethylacetamide (DMA), and 11 g of isopropylalcohol. The reaction solution was purged with nitrogen, 0.13 g of AMBNpolymerization initiator was added, and nitrogen was bubbled through theslurry for 60 minutes before heating it in an oil bath at 67° C. forabout 18 hours. The reaction solution was cooled and diluted with waterto form a clear solution. The reaction solution was then dialyzed forabout 18 hours, cooled, and concentrated to 14.8 weight % solidssolution that was slightly hazy but suitable for coating. The weightaverage molecular weight (M_(w)) of the resulting Inventive reactivepolymer was determined to be 469,000 by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer K Using Styrene Sulfonic AcidSodium Salt and 7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (80:20 mol% Ratio)

6.15 g of styrene sulfonic acid sodium salt and 2.15 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin were weighed out into a 100ml single-neck round bottom flask and dissolved in a solvent mixture of11 g water, 11 g of dimethylacetamide (DMA), and 8.25 g of isopropylalcohol. The reaction solution was purged with nitrogen, and 0.08 g ofAMBN polymerization initiator was added and nitrogen was bubbled throughthe slurry for 60 minutes before heating it in an oil bath at 67° C. forabout 18 hours. The reaction solution was cooled and diluted with waterto form a clear solution. The reaction solution was dialyzed for about60 hours and then concentrated to a 13.06 weight % solids solution thatwas suitable for coating. The weight average molecular weight (Mw) ofthe resulting Inventive reactive polymer was 258,000 as determined bysize exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer L Using Styrene Sulfonic AcidSodium Salt, Methacrylic Acid, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (50:30:20 mol % Ratio)

4.50 g of styrene sulfonic acid sodium salt, 1.13 g of methacrylic acid,and 2.52 g of 7-(2-methacryloyloxyethoxy)-4-methylcoumarin were weighedout in a 250 ml single-neck round-bottom flask dissolved in a solventmixture of 12 g of water, 12 g of dimethylacetamide (DMA), and 4.15 g ofisopropyl alcohol. 0.08 g of AMBN polymerization initiator was added andnitrogen was bubbled through the slurry for 30 minutes before heating inan oil bath at 65° C. for about 18 hours. The reaction mixture wascooled and diluted with water to form a clear solution. The reactionsolution was dialyzed for about 18 hours and then concentrated to a15.53 weight % solids solution that was suitable for coating. The weightaverage molecular weight (M_(w)) of the resulting Inventive reactivepolymer was 437,000 as determined by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer M Using2-Acrylamido-2-methyl-1-propanesulfonic Acid and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (80:20 mol % Ratio)

6.15 g of 2-acrylamido-2-methyl-1-propanesulfonic acid and 2.14 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin were weighed out into a 100ml single neck round bottom flask and dissolved in a solvent mixture of11 g water, 11 g of dimethylacetamide (DMA), and 8.25 g of isopropylalcohol. The reaction solution was purged with nitrogen, 0.08 g of AMBNpolymerization initiator were added, and nitrogen was bubbled throughthe slurry for 60 minutes before heating it in an oil bath at 67° C. forabout 18 hours. The reaction solution was cooled and diluted with waterto form a clear solution that was dialyzed for about 60 hours and thenconcentrated to a 15.68 weight % solids solution that was suitable forcoating. The weight average molecular weight (Mw) of the resultingInventive reactive polymer was 48,900 as determined by size exclusionchromatography (SEC).

Preparation of Inventive Reactive Polymer N Using2-Acrylamido-2-methyl-1-propanesulfonic acid, Methacrylic Acid, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (50:30:20 mol % Ratio)

4.50 g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 1.12 g ofmethacrylic acid, and 2.5 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomers were weighed outin a 250 ml single-neck round-bottom flask dissolved in a solventmixture of 11 g of water, 11 g of dimethylacetamide (DMA), and 4.5 g ofisopropyl alcohol. The reaction mixture was purged with nitrogen, 0.08 gof AMBN polymerization initiator was added, and nitrogen was bubbledthrough the slurry for 30 minutes before heating in an oil bath at 65°C. for about 18 hours. The reaction solution was cooled and diluted withwater to form a clear solution. The reaction solution was dialyzed forabout 18 hours and then concentrated to a 14.41 weight % solids solutionthat was suitable for coating. The weight average molecular weight(M_(w)) of the resulting Inventive reactive polymer was 322,000 asdetermined by size exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer 0 Using2-Acrylamido-2-methyl-1-propanesulfonic acid and 2-Cinnamoyl-ethylmethacrylate (80:20 mol % Ratio)

4.15 g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 1.30 g of2-cinnamoyl-ethyl methacrylate monomer, and 0.027 g of AMBNpolymerization initiator were weighed out in a 100 ml single-neckround-bottom flask and dissolved in a solvent mixture of 5.45 g ofwater, 5.45 g of methyl ethyl ketone (MEK), and 4.45 g of isopropylalcohol. Nitrogen was bubbled through the reaction solution for 30minutes before heating in an oil bath at 70° C. for about 18 hours. Thereaction solution was cooled and diluted with water to forming a cloudysolution. The reaction solution was dialyzed for about 18 hours and thenconcentrated to a 15.98 weight % solids solution that was suitable forcoating. The weight average molecular weight (M_(w)) of the Inventivereactive polymer was 51,800 as determined by size exclusionchromatography (SEC).

Preparation of Inventive Reactive Polymer P Using2-Acrylamido-2-methyl-1-propanesulfonic acid, Methacrylic Acid, and2-Cinnamoyl-ethyl methacrylate (50:30:20 mol % Ratio)

2.59 g of 2-acrylamido-2-methyl-1-propanesulfonic acid, 0.65 g ofmethacrylic acid, 1.30 g of 2-cinnamoyl-ethyl methacrylate monomer, and0.045 g of AMBN polymerization initiator were weighed out in a 100 mlsingle-neck round-bottom flask and dissolved in a solvent mixture of8.58 g of water, 8.58 g of methyl ethyl ketone (MEK), and 8.58 g ofisopropyl alcohol. Nitrogen was bubbled through the reaction solutionfor 30 minutes before heating it in an oil bath at 70° C. for about 18hours. The reaction solution was cooled and diluted with water toforming a clear solution. The reaction solution was then dialyzed forabout 18 hours and concentrated to an 18.64 weight % solids solutionthat was suitable for coating. The weight average molecular weight (Mw)of the Inventive reactive polymer was 62,200 as determined by sizeexclusion chromatography (SEC).

Preparation of Inventive Polymer Q Using 3-Sulfopropyl MethacrylatePotassium Salt, N-vinyl-2-pyrrolidone, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (50:30:20 mol % Ratio)

4.93 g of 3-sulfopropyl methacrylate potassium salt, 1.33 g ofN-vinyl-2-pyrrolidone, and 2.31 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin were weighed out in a 250ml single-neck round-bottom flask and dissolved in a solvent mixture of11 g of water, 11 g of dimethyl acetamide (DMA), and 8.25 g of isopropylalcohol. Then, 0.09 g of AMBN polymerization initiator was added andnitrogen was bubbled through the slurry for 60 minutes before heating itin an oil bath at 65° C. for about 18 hours. The reaction solution wascooled and diluted with water to form a clear solution that was dialyzedfor about 24 hours and then concentrated to a 12.56 weight % solidssolution that was suitable for coating. The weight average molecularweight (M_(w)) of the resulting Inventive reactive polymer was 112,000as determined by size exclusion chromatography (SEC).

Preparation of Inventive Polymer R Using 3-Sulfopropyl MethacrylatePotassium Salt, N-vinyl-2-pyrrolidone, Methacrylic Acid, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (20:30:30:20 mol % Ratio)

1.04 g of 3-sulfopropyl methacrylate potassium salt, 0.70 g ofN-vinyl-2-pyrrolidone, 0.55 g of methacrylic acid, and 1.22 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin were weighed out into a 250ml single-neck round-bottom flask and dissolved in a solvent mixture of4.5 g of water, 5.5 g of dimethyl acetamide (DMA), and 4.13 g ofisopropyl alcohol. Then, 0.04 g of AMBN polymerization initiator wasadded and nitrogen was bubbled through the slurry for 60 minutes beforeheating it in an oil bath at 65° C. for about 18 hours. The reactionsolution was cooled and diluted with water to form a clear solution thatwas dialyzed for about 24 hours and then concentrated to an 11.46 weight% solids solution that was suitable for coating. The weight averagemolecular weight (Mw) of the resulting Inventive reactive polymer was608,000 as determined by size exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer S Using 3-SulfopropylMethacrylate Potassium Salt, 2-Hydroxyethyl Methacrylate, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (50:30:20 mol % Ratio)

4.00 g of 3-sulfopropyl methacrylate potassium salt was dissolved in 10g of distilled water in a 250 ml single-neck round-bottom flask,followed by addition of 1.27 g of 2-hydroxyethyl methacrylate and 10 gof isopropyl alcohol. Then, 1.87 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomer and 10 g ofdimethylacetamide (DMA) were added, followed by 0.07 g of AMBNpolymerization initiator. Nitrogen was bubbled through the slurry for 30minutes before heating it in an oil bath at 65° C. for about 18 hours.The reaction solution was cooled and diluted with water to form a clearsolution. The reaction solution was then dialyzed for about 18 hours indistilled water and concentrated to a 14.94 weight % solids solutionthat was suitable for coating. The weight average molecular weight(M_(w)) of the resulting Inventive reactive polymer was 269,000 asdetermined by size exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer T Using 3-SulfopropylMethacrylate Potassium Salt, 2-Hydroxyethyl Methacrylate, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (10:70:20 mol % Ratio)

1.00 g of 3-sulfopropyl methacrylate potassium salt was dissolved in 10g of distilled water in a 250 ml single-neck round-bottom flask,followed by addition of 3.7 g of 2-hydroxyethyl methacrylate, 10 g ofisopropyl alcohol, 2.34 g of7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomer, 10 g ofdimethylacetamide (DMA), and 0.07 g of AMBN polymerization initiator.Nitrogen was bubbled through the slurry for 30 minutes before heating itin an oil bath at 65° C. for about 18 hours. The reaction solution wascooled and diluted with water to form a clear solution. The reactionsolution was then dialyzed for about 18 hours in distilled water andthen concentrated to a 13.76 weight % solids solution that was suitablefor coating. The weight average molecular weight (Mw) of the resultingInventive reactive polymer was 127,000 as determined by size exclusionchromatography (SEC).

Preparation of Inventive Reactive Polymer U Using 3-SulfopropylMethacrylate Potassium Salt, Maleic Anhydride, and7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (50:30:20 mol % Ratio)

4.00 g of 3-sulfopropyl methacrylate potassium salt was dissolved in 10g of distilled water in a 250 ml single-neck round-bottom flask,followed by addition of 0.96 g of maleic anhydride, 10 g of isopropylalcohol, 1.87 g of 7-(2-methacryloyloxyethoxy)-4-methylcoumarin monomer,10 g of dimethylacetamide (DMA), and 0.07 g of AMBN polymerizationinitiator. Nitrogen was bubbled through the slurry for 30 minutes beforeheating it in an oil bath at 65° C. for about 18 hours. The reactionsolution was cooled and diluted with water to form a clear solution. Thereaction solution was then dialyzed for about 18 hours in distilledwater and then concentrated to a 13.87 weight % solids solution that wassuitable for coating. The weight average molecular weight (M_(w)) of theresulting Inventive reactive polymer was 100,000 as determined by sizeexclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer V Using 3-SulfopropylMethacrylate Potassium Salt, Acrylamide, and 2-Cinnamoyl-ethylmethacrylate (50:30:20 mol % Ratio)

In a 100 ml single-neck round-bottom flask, 4.26 g of 3-sulfopropylmethacrylate potassium salt, 0.80 g of acrylamide, 1.95 g of2-cinnamoyl-ethyl methacrylate, and 147 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture of 33.17 g of water and33.17 g of isopropyl alcohol (IPA). The reaction mixture was purged withnitrogen, capped with a septum, and set in a preheated oil bath at 70°C. overnight. The reaction mixture was then cooled and placed in adialysis bag with MWCO of 3500 and dialyzed for about 18 hours, forminga gel-like product that dissolved upon addition of 0.47 g of a 45 weight% potassium hydroxide solution. The composition was then evaporated to aconcentration of 11.07 weight % solids. The weight average molecularweight (M_(w)) of the resulting Inventive reactive polymer was 181,000as determined by size exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer W Using 3-SulfopropylMethacrylate Potassium Salt, Acrylamide, and 2-Cinnamoyl-ethylmethacrylate (10:70:20 mol % Ratio)

In a 100 ml single-neck round-bottom flask, 0.92 g of 3-sulfopropylmethacrylate potassium salt, 1.87 g of acrylamide, 1.95 g of2-cinnamoyl-ethyl methacrylate, and 95 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture of 21.33 g of water and21.33 g of isopropyl alcohol (IPA). The reaction mixture was purged withnitrogen, capped with a septum, and set into a preheated oil bath at 70°C. overnight. The reaction mixture was then cooled and placed in adialysis bag with MWCO of 3500 and dialyzed for about 18 hours, forminga cloudy but stable dispersion. The composition was then evaporated to aconcentration of 13.24 weight % solids.

Preparation of Inventive Reactive Polymer X Using 3-SulfopropylMethacrylate Potassium Salt, 2-Hydroxyethyl Methacrylate, and2-Cinnamoyl-ethyl methacrylate (50:30:20 mol % Ratio)

In a 100 ml single-neck round-bottom flask, 3.08 g of 3-sulfopropylmethacrylate potassium salt, 0.98 g of 2-hydroxyethyl methacrylate, 1.30g of 2-cinnamoyl-ethyl methacrylate, and 54 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture of 7.15 g of water, 7.15 gof methyl ethyl ketone (MEK), and 7.15 g of isopropyl alcohol (IPA). Thereaction mixture was capped with a septum, purged with nitrogen for 30minutes, and set in a preheated oil bath at 70° C. for about 18 hours.The reaction mixture was cooled and placed in a dialysis bag with MWCOof 3500 and dialyzed in distilled water for about 18 hours. Thecomposition was then evaporated to a concentration of 13.78 weight %solids. The weight average molecular weight (Mw) of the resultingInventive reactive polymer was 69,300 as determined by size exclusionchromatography (SEC).

Preparation of Inventive Reactive Polymer Y Using 3-SulfopropylMethacrylate Potassium Salt, 2-Hydroxyethyl Methacrylate, and2-Cinnamoyl-ethyl methacrylate (10:70:20 mol % Ratio)

In a 100 ml single-neck round-bottom flask, 0.92 g of 3-sulfopropylmethacrylate potassium salt, 3.42 g of 2-hydroxyethyl methacrylate, 1.95g of 2-cinnamoyl-ethyl methacrylate, and 63 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture of 8.39 g of water, 8.39 gof methyl ethyl ketone (MEK), and 8.39 g of isopropyl alcohol (IPA). Thereaction mixture was capped with a septum, purged with nitrogen for 30minutes, and set in a preheated oil bath at 70° C. for about 18 hours.The reaction mixture was then cooled and placed in a dialysis bag withMWCO of 3500 and dialyzed in distilled water for about 18 hours. Thecomposition was then evaporated to a concentration of 12.85 weight %solids. The weight average molecular weight (Mw) of the resultingInventive reactive polymer was 542,000 as determined by size exclusionchromatography (SEC).

Preparation of Inventive Reactive Polymer Z Using 3-SulfopropylMethacrylate Potassium Salt, Maleic Anhydride, and 2-CinnamoylethylMethacrylate (50:30:20 mol % Ratio)

In a 100 ml single-neck round-bottom flask, 3.08 g of 3-sulfopropylmethacrylate potassium salt, 0.74 g of maleic anhydride, 1.30 g of2-cinnamoyl-ethyl methacrylate, and 51 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture consisting of 6.83 g ofwater, 6.83 g of methyl ethyl ketone (MEK), and 6.83 g of isopropylalcohol (IPA). The reaction mixture was capped with a septum, purgedwith nitrogen for 30 minutes, and set in a preheated oil bath at 70° C.for about 18 hours. The reaction mixture was then cooled and placed in adialysis bag with MWCO of 3500 and dialyzed in distilled water for about18 hours. The composition was then evaporated to a concentration of14.20 weight % solids. The weight average molecular weight (M_(w)) ofthe resulting Inventive reactive polymer was 68,500 as determined bysize exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer AA Using 3-SulfopropylMethacrylate Potassium Salt, Maleic Anhydride, and 2-CinnamoylethylMethacrylate (10:70:20 mol % Ratio)

In a 100 ml single-neck round-bottom flask, 0.92 g of 3-sulfopropylmethacrylate potassium salt, 2.57 g of maleic anhydride, 1.95 g of2-cinnamoyl-ethyl methacrylate, and 54 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture consisting of 7.25 g ofwater, 7.25 g of methyl ethyl ketone (MEK), and 7.25 g of isopropylalcohol (IPA). The reaction mixture was capped with a septum, purgedwith nitrogen for 30 minutes, and set in a preheated oil bath at 70° C.for about 18 hours. The reaction mixture was then cooled and placed in adialysis bag with MWCO of 3500 and dialyzed in distilled water for about18 hours. The composition was then evaporated to a concentration of13.21 weight % solids. The weight average molecular weight (M_(w)) ofthe resulting Inventive reactive polymer was 50,500 as determined bysize exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer AB Using 3-SulfopropylMethacrylate Potassium Salt, Vinyl Phosphonic Acid, and 2-Cinnamoylethylmethacrylate (50:30:20 mol % Ratio)

In a 100 ml single-neck round-bottom flask, 1.85 g of 3-sulfopropylmethacrylate potassium salt, 1.35 g of vinyl phosphonic acid, 1.30 g of2-cinnamoyl-ethyl methacrylate, and 45 mg of AMBN polymerizationinitiator were dissolved in a solvent mixture consisting of 8.50 g ofwater, 8.50 g of methyl ethyl ketone (MEK), and 8.50 g of isopropylalcohol (IPA). The reaction mixture was capped with a septum, purgedwith nitrogen for 30 minutes, and set in a preheated oil bath at 70° C.for about 18 hours. The reaction mixture was cooled and placed in adialysis bag with MWCO of 3500 and dialyzed in distilled water for about18 hours. The composition was then evaporated to a concentration of18.33 weight % solids. The weight average molecular weight (M_(w)) ofthe resulting Inventive reactive polymer was 26,600 as determined bysize exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer AC Using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, and2-(2,3-Diphenyl-2-cyclopropene-1-carboxyl)-ethyl methacrylate (50:30:20mol % Ratio)

3.0 g of 3-sulfopropyl methacrylate potassium salt was dissolved in 16 gof distilled water in a 250 ml single-neck round-bottom flask followedby addition of a solution of 1.70 g of2-(2,3-diphenyl-2-cyclopropene-1-carboxyl)-ethyl methacrylate dissolvedin 16 g of MEK to form a two-phase mixture. A solution of 0.63 g ofmethacrylic acid dissolved in 16 g of isopropyl alcohol was then addedand the solution became a single phase, followed by addition of 0.11 gof AMBN polymerization initiator. The reaction solution was capped witha septum, purged with nitrogen for 30 minutes, and then set in apreheated oil bath at 70° C. for about 18 hours. The reaction solutionwas cooled and diluted with water to form a clear solution. The solutionwas dialyzed for about 18 hours and then concentrated to an 11.76 weight% solids solution that was suitable for coating.

Preparation of Inventive Reaction Polymer AD Using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, and2-(2,3-Diphenyl-2-cyclopropene-1-carboxyl)-ethyl methacrylate (10:70:20mol % Ratio)

0.53 g of 3-sulfopropyl methacrylate potassium salt was dissolved in 10g of distilled water in a 250 ml single-neck round-bottom flask followedby addition of a solution of 1.50 g of2-(2,3-diphenyl-2-cyclopropene-1-carboxyl)-ethyl methacrylate monomerdissolved in 10 g of MEK to form a two-phase mixture. A solution of 1.30g of methacrylic acid dissolved in 10 g of isopropyl alcohol was thenadded and the solution became a single phase, followed by addition of0.07 g of AMBN polymerization initiator. The solution was capped with aseptum, purged with nitrogen for 30 minutes, and set in a preheated oilbath at 70° C. for about 18 hours. The reaction solution was cooled anddiluted with water to form a clear solution that was dialyzed for about18 hours and then concentrated to a 12.64 weight % solids solution thatwas suitable for coating. The weight average molecular weight (Mw) ofthe resulting Inventive reactive polymer was 61,800 as determined bysize exclusion chromatography (SEC).

Preparation of Invention Reactive Polymer AE Using 3-SulfopropylMethacrylate Potassium Salt and N-(2-(methacryloxy)ethyl)Dimethylmaleimide (80:20 mol % Ratio)

In a 100 ml single neck round bottom flask, 4.93 g of 3-sulfopropylmethacrylate potassium salt, 1.19 g of N-(2-(methacryloxy)ethyl)dimethylmaleimide, and 61 mg of AMBN were dissolved in a solvent mixtureconsisting of 8.16 g of water, 8.16 g of methyl ethyl ketone (MEK), and8.16 g of isopropyl alcohol (IPA). The reaction mixture was capped witha septum, purged with nitrogen for 30 minutes, and set in a preheatedoil bath at 70° C. for about 18 hours. The reaction mixture was cooledand placed in a dialysis bag with MWCO of 3500 and dialyzed in distilledwater for about 18 hours. The contents were then evaporated to aconcentration of 16.84 weight % solids. The weight average molecularweight (Mw) of the resulting Invention Reactive Polymer AE was 110,000as determined by size exclusion chromatography (SEC).

Preparation of Inventive Reactive Polymer AF Using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, andN-(2-(methacryloxy)ethyl) Dimethylmaleimide (50:30:20 mol % Ratio)

In a 100 ml single neck round bottom flask, 3.08 g of 3-sulfopropylmethacrylate potassium salt, 0.65 g of methacrylic acid, 1.19 g ofN-(2-(methacryloxy)ethyl) dimethylmaleimide, and 49 mg of AMBN weredissolved in a solvent mixture consisting of 6.56 g of water, 6.56 g ofmethyl ethyl ketone (MEK), and 6.56 g of isopropyl alcohol (IPA). Thereaction mixture was capped with a septum, purged with nitrogen for 30minutes, and set in a preheated oil bath at 70° C. for about 18 hours.The reaction mixture was cooled and placed in a dialysis bag with MWCOof 3500 and dialyzed in distilled water for about 18 hours. The contentswere then evaporated to a concentration of 15.36 weight % solids. Theweight average molecular weight (Mw) of the resulting Invention ReactivePolymer AF was 93,300 as determined by size exclusion chromatography(SEC).

Preparation of Inventive Reactive Polymer AG Using 3-SulfopropylMethacrylate Potassium Salt, Methacrylic Acid, andN-(2-(methacryloxy)ethyl) Dimethylmaleimide (10:70:20 mol % Ratio)

In a 100 ml single neck round bottom flask, 0.92 g of 3-sulfopropylmethacrylate potassium salt, 2.26 g of methacrylic acid, 1.78 g ofN-(2-(methacryloxy)ethyl) dimethylmaleimide, and 50 mg of AMBN weredissolved in a solvent mixture consisting of 6.61 g of water, 6.61 g ofmethyl ethyl ketone (MEK), and 6.61 g of isopropyl alcohol (IPA). Thereaction mixture was capped with a septum, purged with nitrogen for 30minutes, and set in a preheated oil bath at 70° C. for about 18 hours.The reaction mixture was cooled and placed in a dialysis bag with MWCOof 3500 and dialyzed in distilled water for about 18 hours. The contentswere then evaporated to a concentration of 11.46 weight % solids. Theweight average molecular weight (M_(w)) of the resulting Inventivereactive Polymer AG was 254,000 as determined by size exclusionchromatography (SEC).

Preparation of Polymeric Silver Ion Complexes

For the inventive polymers described above, a water soluble andwater-coatable polymer silver ion complex was formed as follows:

A quantity of Inventive reactive polymer solution sufficient to provide5.0 g of 8.5 weight % of reactive polymer was added to a clear glassvessel, followed by any additional make-up water. With vigorousstirring, 0.614 g of 2.0 molar silver nitrate solution was addeddropwise. A stable colorless solution was formed that was generallyclear, but could have some turbidity depending on the type of reactivepolymer. A surfactant such as Dupont Capstone FS-35 or TERGITOL® 15-S-9was added at between 0.05 and 0.5 weight % as a coating aid. Eachresulting solution was easily filtered through a 1 μm glass syringefilter to provide a coating-ready water-soluble formulation (that is, asilver-containing composition).

Preparation of Polymeric Silver Nanoparticle Complexes

A general procedure to from a water-soluble and a water-coatable silvernanoparticle complex with each Inventive reactive polymer describedabove is as follows:

A quantity of polymer solution sufficient to provide 5.0 g of 8.5 weight% reactive polymer was added to a clear glass vessel, followed by anyadditional make-up water. With vigorous stirring, 0.614 g of 2.0 molarsilver nitrate solution was added dropwise. A stable colorless solutionwas formed that was generally clear, but could have some turbiditydepending on the type of reactive polymer. With continued stirring,0.157 g of a freshly prepared 4 weight % dimethylamine borane solutionwas added dropwise. The initially colorless solution immediately becamedeeply colored due to the strong surface plasmon resonance absorption ofthe newly formed silver nanoparticles. The color of the resultingpolymeric silver nanoparticle complex can vary according to the size ofthe silver nanoparticles that were formed. Silver nanoparticles in suchcomplexes with an average diameter size of less than 30 nm had a strongorange to brilliant yellow coloration when prepared by this method ofthe present invention. Larger sized silver nanoparticles in suchcomplexes ranging from 300 nm to 500 nm had much less brilliantcoloration, tending toward muted green and grey colors as the silvernanoparticles take on the neutral grey appearance of larger silvernanoparticles approaching 1 μm in average diameter. A description of theobserved surface plasmon resonance colors are described below in TABLEII.

Preparation of Polymeric Silver Nanoparticle Complexes with High AspectRatio Nanoparticles

The general procedure described above to form a water-soluble andwater-coatable polymeric silver nanoparticle complex can be modified asfollows to produce high aspect ratio platelet silver nanoparticles witha very strong violet to blue surface plasmon resonance absorption.

A quantity of polymer solution sufficient to provide 5.0 g of reactivepolymer was added to a clear glass vessel, followed by any additionalmake-up water. With vigorous stirring, 0.470 g of a freshly prepared 4weight % dimethylamine borane solution was added dropwise. Some foamingcould occur and a colorless solution was formed. With continuedstirring, 0.614 g of 2.0 molar silver nitrate solution was then addeddropwise. The initially colorless solution immediately became deeplycolored due to the strong surface plasmon resonance absorption of thenewly formed silver nanoparticles. The surface plasmon resonance colorindicative of high aspect ratio or platelet shaped silver nanoparticlesis an intense blue, violet or magenta coloration. Transmission electronmicroscopy TEM) analysis shows that a typical platelet silvernanoparticle with an average diameter of 10 nm to 30 nm and a thicknessof 3 nm to 6 nm. Descriptions of the observed surface plasmon resonancecolors are described below in TABLE II.

Coating and Patterning the Polymeric Silver Ion and Silver NanoparticleComplexes

The water-soluble polymeric silver ion and polymeric silver nanoparticlecomplexes described above and listed below in TABLE II were coated andpatterned using ultraviolet (UV) light as follows:

A surfactant such as Dupont Capstone FS-35 or TERGITOL® 15-S-9 was addedto each water-soluble complex at a concentration of between 0.05 weight% and 0.5 weight % and the resulting formulation was passed through a 1μm glass syringe filter. Each of the formulations was then spin coatedat between 2000 and 3000 RPM onto a poly(ethylene terephthalate) (PET)film pre-coated before stretching with a layer of poly(glycidylmethacrylate-co-butyl acrylate) to provide a substrate. Each coating wasthen allowed to dry and age for between 30 and 60 minutes.

Each dried coating was then exposed through a predetermined contact maskto a broadband high pressure UV lamp that was collimated and filteredwith a dichroic mirror with a bandpass of 350 nm to 450 nm. Otherdichroic mirrors with a bandpass of 260 nm to 320 nm or 220 nm to 260 nmcan be used if shorter wavelength UV light is desired. The exposingmasks are made of evaporated chrome on quartz with the high resolutionpatterns made with conventional photolithographic methods capable of sub1 μm resolution. The photo-patternability of each dried complex wasevaluated with a high resolution contact exposure mask with a series offeatures down to 1 μm.

Following UV exposure, each dried coating was then again allowed to agefor 15 to 60 minutes and then baked for 1 minute on a 60° C. hotplatewith vacuum suction. Each sample was then processed for 2 minutes in anagitated bath of distilled water at room temperature to remove anyunexposed polymer complex. After removal from the agitated distilledwater bath, each dried coating was rinsed twice for approximately 5seconds in distilled water to further remove any residual non-exposedcomplex. Optical microscopy was used to evaluate the resolvedline-widths and overall quality of the resulting pattern.

Dried coatings that were exposed through a plain quartz mask to hardenand insolubilize (crosslink) the polymer complex were also prepared forevaluation of their antimicrobial behavior.

TABLE II Description of Inventive Polymeric Silver Ion Complexes andPolymeric Silver Nanoparticle Complexes Appear- Silver ance Average ofHigh Appear- Silver ion Nano- Aspect ance Complex Appearance particleRatio Water- Cross- Monomer Polymer of Silver Patterning of Silver size(nm) Patterning Silver soluble linkable Mol % Molecular Ion with UVNanoparticle by light with UV Nano- Polymer Monomer(s) Monomer RatiosWeight Complex light Complex scattering Radiation particles Inventive ASPMA, MA CIN 2:78:20 1,110,000   turbid beige N/A Inventive B SPMA, MACIN 5:75:20 631,000 slightly yellow-orange  6 nm 3 μm lines dark turbidbrown Inventive C SPMA, MA CIN 10:70:20 219,000 turbid yellow-orange  7nm 2 μm lines purple Inventive D SPMA, MA CIN 30:50:20 113,000 turbidyellow-orange  10 nm 2 μm lines purple Inventive E SPMA, MA CIN 50:30:20 82,000 turbid yellow-orange  12 nm 2 μm lines blue Inventive F SPMA CIN80:20 282,000 turbid 3 μm lines yellow-orange 2 μm lines dull blueInventive G SPMA, MA COUM 10:70:20 422,000 slightly orange  32 nm 3 μmlines turbid Inventive H SPMA, MA COUM 30:50:20 800,000 slightly orange3 μm lines turbid Inventive I SPMA, MA COUM 50:30:20 557,000 clear 3 μmlines olive green 334 nm 4 μm lines dark purple Inventive J SPMA COUM80:20 287,000 clear grey-beige 3 μm lines bright blue Inventive K SSCOUM 80:20 258,000 clear 3 μm lines beige 310 nm 3 μm lines purpleInventive L SS, MA COUM 50:30:20 437,000 clear grey-beige 335 nm 3 μmlines purple Inventive M AMPS COUM 80:20  49,000 slightly 2 μm linesgrey-beige 135 nm 3 μm lines dull blue turbid Inventive N AMPS, MA COUM50:30:20 322,000 slightly grey-beige 298 nm 3 μm lines purple turbidInventive O AMPS CIN 80:20  52,000 turbid dull orange 4 μm lines lightorange* Inventive P AMPS, MA CIN 50:30:20  62,000 slightly orange 4 μmlines light turbid orange* Inventive Q SPMA,VP COUM 50:30:20 112,000clear 2 μm lines dull yellow 152 nm 2 μm lines dark green Inventive RSPMA, COUM 20:30:30:20 608,000 clear grey-beige 375 μm 4 μm lines darkMA,VP brown Inventive S SPMA, HEM COUM 50:30:20 269,000 clear beige 4 μmlines deep blue Inventive T SPMA, HEM COUM 10:70:20 127,000 slightlygrey-beige 4 μm lines dark turbid purple Inventive U SPMA, MD COUM50:30:20 100,000 slightly grey  50 nm 5 μm lines red- turbid orangeInventive V SPMA, AA CIN 50:30:20 181,000 very bright yellow  26 nm 2 μmlines bright turbid yellow* Inventive W SPMA, AA CIN 10:70:20 N/A verydull green N/A turbid Inventive X SPMA, HEM CIN 50:30:20  69,000 turbiddull green 2 μm lines blue Inventive Y SPMA, HEM CIN 10:70:20 542,000Clear olive green 4 μm lines dark purple Inventive Z SPMA, MD CIN50:30:20  69,000 slightly grey 2 μm lines purple turbid Inventive AASPMA, MD CIN 10:70:20  51,000 clear 2 μm lines dull yellow 5 μm linesred Inventive AB SPMA, VPH CIN 30:50:20  27,000 turbid brown-orange  2nm 2 μm lines bright yellow* Inventive AC SPMA, MA DPCP 50:30:20 N/Aturbid grey 4 μm lines Inventive AD SPMA, MA DPCP 10:70:20  62,000 cleargrey 2 μm lines Inventive AE SPMA DMMI 80:20 2 μm lines 2 μm linespurple Inventive AF SPMA, MA DMMI 30:50:20 2 μm lines 2 μm lines purpleInventive AG SPMA, MA DMMI 10:70:20 2 μm lines 2 μm lines brightyellow * Indicates that platelet morphologies were nor formed ** Coatingformulations included 0.85 weight % thioxanthone as a long UVphotosensitizer

Electroless Copper Plating of Patterned Polymeric Silver NanoparticleComplexes:

Preparation of the Electroless Copper Plating Bath:

The following components were dissolved in a glass container that hadbeen cleaned with concentrated nitric acid followed by a thorough rinsewith distilled water to eliminate any trace of metal on the glass. Then,1.8 g of copper (II) sulfate pentahydrate, 6.25 g of tetrasodium EDTA(ethylenediaminetetraacetic acid) tetrahydrate, 0.005 g of potassiumferrocyanide trihydrate, 2.25 g of 37 weight % formaldehyde solution, 80g of distilled water, and 2 to 3 g of 45 weight % sodium hydroxidesolution were mixed to provide an aqueous solution having a pH of 12.8.

In some instances, the catalytic activity of an Inventive polymericsilver nanoparticle complex was evaluated by immersing the driedpatterned coating in an electroless copper plating bath prepared abovefor 6 to 10 minutes. All inventive polymeric silver nanoparticle complexcoatings showed very strong copper plating on all the patternedsurfaces, indicating the presence of highly catalytic amounts of silverion or silver nanoparticles in the patterns. Conductive copper wireswith line widths of less than 5 μm were typically produced.

Antimicrobial Surface Challenge Testing:

A Self-Sanitizing Surface Efficacy Test based on ASTM WK42235 wasconducted using E. coli with a 2 hour dry exposure on 1 inch×1 inch(2.54 cm×2.54 cm) squares of the PET support coated with the silver ioncomplex and silver nanoparticle complex of Inventive reactive polymer F.The dried coatings were exposed for 30 seconds each to collimatedbroadband UV light filtered with a 350 nm to 450 nm bandpass dichroicfilter. A 1 to 2 log reduction in colony forming units (CFU) per carrierwas observed for the coatings of both the polymeric silver ion complexand the polymeric silver nanoparticle complex of Inventive reactivepolymer F relative to a coating of Inventive reactive polymer Fcontaining no silver. These results indicate a significant antimicrobialresponse from both the complexes containing ionic silver or silvernanoparticles in the patterned and crosslinked coatings prepared usingInventive reactive polymer F.

High Resolution Patterning to Form Antimicrobial Surfaces withResistance to Microbial Colonization and Bio-film Formation:

High resolution chrome-on-quartz masks where prepared to produceSHARKLET™ AF patterns with 1.5 to 2 μm lines and spaces as described inU.S. Patent Application Publication 2010/0226943A1 and U.S. Pat. No.7,650,848B2 (Brennan et al.) and U.S. Pat. No. 7,143,709B2 (Brennan etal.). Inventive polymeric silver ion and polymeric silver nanoparticlecomplexes containing Inventive reactive polymers E and V were preparedand coated on the primed PET substrate described above for generalpatterning procedures. Each dried coating was exposed through theSHARKLET™ AF mask with collimated broadband UV light filtered with a 350nm to 450 nm bandpass dichroic filter and processed with an agitateddistilled water bath as described above for the general photopatterningprocedure.

Both the Invention polymeric silver ion and polymeric silvernanoparticle complexes were successfully used to reproduce theapproximately 1.5 to 2 μm line-width features of the SHARKLET™ AF mask.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

The invention claimed is:
 1. A method for providing a silver-containingarticle, the method comprising: disposing a silver-containingcomposition onto a first supporting side of a substrate, thesilver-containing composition comprising a water-soluble complex of areactive polymer with reducible silver ions, the reactive polymercomprising: (a) greater than 1 mol % of recurring units comprisingsulfonic acid or sulfonate groups, (b) at least 5 mol % of recurringunits comprising a pendant group capable of crosslinking via [2+2]photocycloaddition, and optionally (c) at least 1 mol % of recurringunits comprising a pendant amide, hydroxyl, lactam, phosphonic acid, orcarboxylic acid group, all amounts based on the total recurring units inthe reactive polymer.
 2. The method of claim 1, wherein the reactivepolymer comprises at least 5 mol % of the recurring units comprisingsulfonic acid or sulfonate groups based on the total amounts ofrecurring units in the reactive polymer.
 3. The method of claim 1,wherein the reactive polymer comprises at least 5 mol % and up to andincluding 50 mol % of the recurring units comprising a pendant groupcapable of crosslinking via [2+2] photocycloaddition based on the totalrecurring units in the reactive polymer.
 4. The method of claim 1,wherein the reactive polymer comprises at least 1 mol % and up to andincluding 93 mol % of recurring units comprising a pendant hydroxyl,amide, or carboxylic acid group, based on the total recurring units inthe reactive polymer.
 5. The method of claim 1, wherein the recurringunits comprising a pendant group capable of crosslinking via [2+2]photocycloaddition comprise: (i) a photosensitive —C(═O)—CR═CR¹—Y groupwherein R and R¹ are independently hydrogen or an alkyl group having 1to 7 carbon atoms, a 5- to 6-membered cycloalkyl group, an alkoxy grouphaving 1 to 7 carbon atoms, a phenyl group, or a phenoxy group, and Y isan aryl or heteroaryl group; (ii) a photosensitive, non-aromaticunsaturated carbocyclic group; (iii) a photosensitive, aromatic ornon-aromatic heterocyclic group comprising a carbon-carbon double bondthat is conjugated with an electron withdrawing group; (iv) aphotosensitive non-aromatic unsaturated heterocyclic group comprisingone or more amide groups that are conjugated with a carbon-carbon doublebond, which photosensitive non-aromatic unsaturated heterocyclic groupis linked to the water-soluble backbone at an amide nitrogen atom, or(v) a photosensitive substituted or unsubstituted 1,2-diarylethylenegroup.
 6. The method of claim 1, wherein the reactive polymer is one ofthe following: poly(3-sulfopropyl methacrylate potassiumsalt-co-2-cinnamoyl-ethyl methacrylate) (80:20 mol %);poly(3-sulfopropyl methacrylate-co-methacrylic acid-co-2-cinnamoyl-ethylmethacrylate) (2:78:20 mol %); poly(3-sulfopropylmethacrylate-co-methacrylic acid-co-2-cinnamoyl-ethyl methacrylate)(5:75:20 mol %); poly(3-sulfopropyl methacrylate-co-methacrylicacid-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %);poly(3-sulfopropyl methacrylate-co-methacrylic acid-co-2-cinnamoyl-ethylmethacrylate) (30:50:20 mol %); poly(3-sulfopropyl methacrylatepotassium salt-co-methacrylic acid-co-2-cinnamoyl-ethyl methacrylate)(50:30:20 mol %); poly(3-sulfopropyl methacrylate potassiumsalt-co-2-hydroxyethyl methacrylate acid-co-2-cinnamoyl-ethylmethacrylate) (50:30:20 mol %); poly(3-sulfopropyl methacrylatepotassium salt-co-acrylamide-co-2-cinnamoyl-ethyl methacrylate)(50:30:20 mol %); poly(3-sulfopropyl methacrylate potassiumsalt-co-N-vinyl-2-pyrrolidone-co-2-cinnamoyl-ethyl methacrylate)(50:30:20 mol %); poly(3-sulfopropyl methacrylate potassiumsalt-co-maleic anhydride-co-2-cinnamoyl-ethyl methacrylate) (50:30:20mol %); poly(3-sulfopropyl methacrylate potassium salt-co-vinylphosphonic acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-2-cinnamoyl-ethylmethacrylate) (80:20 mol %); poly(2-acylamido-2-methyl-1-propanesulfonicacid-co-methacrylic acid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20mol %); poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-methacrylicacid-co-2-cinnamoyl-ethyl methacrylate) (10:70:20 mol %); poly(styrenesulfonic acid sodium salt-co-2-cinnamoyl-ethyl methacrylate) (80:20 mol%); poly(styrene sulfonic acid sodium salt-co-methacrylicacid-co-2-cinnamoyl-ethyl methacrylate) (50:30:20 mol %);poly(3-sulfopropyl methacrylate potassiumsalt-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);poly(3-sulfopropyl methacrylate potassium salt-co-methacrylicacid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);poly(3-sulfopropyl methacrylate potassium salt-co-methacrylicacid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (10:70:20 mol %);poly(styrene sulfonic acid sodiumsalt-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);poly(styrene sulfonic acid sodium salt-co-methacrylicacid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);poly(2-acylamido-2-methyl-1-propanesulfonicacid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (80:20 mol %);poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-methacrylicacid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol %);poly(2-acylamido-2-methyl-1-propanesulfonic acid-co-methacrylicacid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (10:70:20 mol %);poly(3-sulfopropyl methacrylate potassiumsalt-co-acrylamide-co-7-(2-methacryloxyethoxy)-4-methylcoumarin)(50:30:20 mol %); poly(3-sulfopropyl methacrylate potassiumsalt-co-2-hydroxyethylmethacrylate-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol%); poly(3-sulfopropyl methacrylate potassium salt-co-maleicanhydride-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (50:30:20 mol%); poly(3-sulfopropyl methacrylate potassiumsalt-co-N-vinyl-2-pyrrolidone-co-7-(2-methacryloxyethoxy)-4-methylcoumarin)(50:30:20 mol %); poly(3-sulfopropyl methacrylate potassiumsalt-co-N-vinyl-2-pyrrolidone-co-methacrylicacid-co-7-(2-methacryloxyethoxy)-4-methylcoumarin) (20:30:30:20 mol %);poly (3-sulfopropyl methacrylate-co-N-(2-(methacryloxy)ethyl)dimethylmaleimide) (20:80 mol %); poly (3-sulfopropylmethacrylate-co-methacrylic acid-co-N-(2-(methacryloxy)ethyl)dimethylmaleimide) (50:30:20 mol %); poly (3-sulfopropylmethacrylate-co-methacrylic acid-co-N-(2-(methacryloxy)ethyl)dimethylmaleimide) (10:70:20 mol %); poly (styrene sulfonic acid sodiumsalt-co-methacrylic acid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide)(50:30:20 mol %); poly (styrene sulfonic acid sodium salt-co-methacrylicacid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (10:70:20 mol %);poly (2-acylamido-2-methyl-1-propanesulfonic acid -co-methacrylicacid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (50:30:20 mol %);poly (2-acylamido-2-methyl-1-propanesulfonic acid -co-methacrylicacid-co-N-(2-(methacryloxy)ethyl) dimethylmaleimide) (10:70:20 mol %);poly(3-sulfopropyl methacrylate sodium salt-co-methacrylicacid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethylmethacrylate) (10:70:20 mol %); poly(styrene sulfonic acid sodiumsalt-co-methacrylicacid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethylmethacrylate) (10:70:20 mol %); andpoly(2-acrylamido-2-methyl-1-propanesulfonic acid-co-methacrylicacid-co-2-(2,3-diphenyl-2-cyclopropene-1-carbonyloxy) ethylmethacrylate) (10:70:20 mol %).
 7. The method of claim 1, wherein thesubstrate has an integrated transmittance of at least 90%.
 8. The methodof claim 1, comprising disposing the silver-containing composition ontoa supporting side of the substrate in a patternwise fashion using aflexographic printing member.
 9. The method of claim 1, furthercomprising: either immediately before or immediately after disposing thesilver-containing composition onto the substrate, reducing the reduciblesilver ions in the water-soluble complex to form silver nanoparticles inthe water-soluble complex.
 10. The method of claim 9, furthercomprising: after reducing the reducible silver ions, photoexposing thewater-soluble complex containing the silver nanoparticles to form acrosslinked water-insoluble complex comprising the silver nanoparticles.11. The method of claim 10, comprising: photoexposing the water-solublecomplex containing the silver nanoparticles in a patternwise fashion onthe substrate.
 12. The method of claim 9, comprising: reducing thesilver ions in the water-soluble complex to form silver nanoparticleshaving an average diameter of at least 2 nm and up to and including 500nm.
 13. The method of claim 11, further comprising, after photoexposingthe water-soluble complex to form the crosslinked water-insolublecomplex containing silver nanoparticles, heating the crosslinkedwater-insoluble complex containing silver nanoparticles at a temperaturesufficient to further crosslink the crosslinked water-insoluble complexcontaining the silver nanoparticles.
 14. The method of claim 11, furthercomprising, after photoexposing the water-soluble complex to form thecrosslinked water-insoluble complex containing silver nanoparticles,removing any remaining water-soluble complex from the substrate.
 15. Themethod of claim 14, further comprising: electrolessly plating thecrosslinked water-insoluble complex using an electrically-conductivemetal.
 16. The method of claim 1, comprising: disposing thesilver-containing composition onto the first supporting side of asubstrate, either immediately before or immediately after disposing thesilver-containing composition onto the first supporting side of thesubstrate, reducing the reducible silver ions in the water-solublecomplex to form silver nanoparticles in the water-soluble complex on thefirst supporting side of the substrate, disposing the same or differentsilver-containing composition onto an opposing second supporting side ofthe substrate, either immediately before or immediately after disposingthe silver-containing composition onto the opposing second supportingside of the substrate, reducing the reducible silver ions in thewater-soluble complex to form silver nanoparticles in the water-solublecomplex on the opposing second supporting side of the substrate, andphotoexposing the water-soluble complex containing the silvernanoparticles on either or both of the first supporting side andopposing second supporting side of the substrate, to form a crosslinkedwater-insoluble complex comprising the silver nanoparticles on either orboth of the first supporting side and opposing supporting side of thesubstrate, and optionally, removing any remaining water-soluble complexfrom both the first supporting side and the opposing second supportingside of the substrate.
 17. The method of claim 16 further comprising:removing any remaining water-soluble complex from both the firstsupporting side and the opposing second supporting side of thesubstrate, and electrolessly plating the crosslinked water-insolublecomplex on either or both of the first supporting side and the secondopposing supporting side of the substrate using anelectrically-conductive metal.
 18. The method of claim 16, comprising:photoexposing the water-soluble complex containing the silvernanoparticles on either or both of the first supporting side and theopposing second supporting side in a patternwise fashion on thesubstrate.
 19. The method of claim 16, comprising: reducing the silverions in the water-soluble complex on either or both the first supportingside and the opposing second supporting side to form silvernanoparticles having an average diameter of at least 2 nm and up to andincluding 500 nm.
 20. The method of claim 16, wherein the substrate is acontinuous web of transparent polymeric film having an integratedtransmittance of at least 80%.